Novel iron-based complex and application in electrochemical energy storage

Abstract

The invention provides a series of novel metal-based complexes with oxidation-reduction activity, and the structural formula of the novel iron-based complexes is shown as the following formula: wherein the novel iron-based complexes are substituted or unsubstituted 5-12-membered nitrogen-containing heteroaromatic rings, substituted or unsubstituted 5-12-membered oxygen-containing heteroaromatic rings, substituted or unsubstituted 5-12-membered sulfur-containing heteroaromatic rings and carbon carbene structures; m1 is selected from the following groups: Fe (II) and Fe (III); x and y are selected from the following groups: 0-20; the novel iron-based complex is electrically neutral. The invention also researches the application of the novel metal-based complexes in electrochemical energy storage systems such as aqueous flow batteries.

Description

Technical Field

[0001] The present invention belongs to the field of battery technology, specifically relates to a series of novel iron-based complexes with redox activity, and studies their application in electrochemical energy storage systems such as aqueous liquid flow batteries. Background Art

[0002] The non-renewable and highly polluting nature of traditional energy sources hinders the development of a sustainable energy structure and social system. At the same time, rapidly developing economies and societies are placing ever-higher demands on energy. The continuous development and implementation of diverse clean energy sources, including solar, wind, hydro, and molten salt, to meet the needs of production and daily life are placing higher demands on energy storage equipment. Energy storage systems must not only be able to smooth out peaks and valleys to ensure grid stability but also offer cost advantages to achieve the economical conversion of clean energy.

[0003] The concept of flow batteries was first proposed in 1974. Flow batteries have attracted renewed attention from researchers in recent years due to their potential for application in stationary, large-scale energy storage systems, given their cost, safety, and reliability. Various flow battery systems have been developed, generally categorized as aqueous and non-aqueous (organic solvent) flow batteries based on the properties of the electrolyte. Aqueous flow batteries, based on water-soluble active materials, offer greater safety and environmental benefits compared to organic systems, making them more suitable for large-scale energy storage applications. However, the solubility of water-soluble materials is often low, with most having a solubility of less than 1.0 M. Furthermore, the choice of active materials, particularly the positive electrode, is severely limited due to solubility and electrolyte window constraints. Aside from the more mature all-vanadium flow batteries and metal-halide flow batteries, commonly used positive electrodes fall into three main categories: ferrocenium-based, iron / ferrocyanide-based, and TEMPO-based. Summary of the Invention

[0004] The first object of the present invention is to provide a novel iron-based complex.

[0005] To this end, the above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0006] A novel iron-based complex, the structural formula of the novel iron-based complex is shown below:

[0007]

[0008] in, is a substituted or unsubstituted 5-12 membered nitrogen-containing heteroaromatic ring, a substituted or unsubstituted 5-12 membered oxygen-containing heteroaromatic ring, a substituted or unsubstituted 5-12 membered sulfur-containing heteroaromatic ring, or a carbon carbene structure;

[0009] M 1Selected from the group consisting of Fe(II), Fe(III)

[0010] R 1 、R 2 、R 3 、R 4 , R 5 , are each independently selected from the following group: H, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted 5-12 membered heterocycloalkyl or aryl, substituted or unsubstituted C6-C10 aryl, mercapto (-S - or -SH), nitro (-NO2), cyano (-CN), halogen (-F or -Cl or -Br), -COOY, -SO3Y, -PO3Y, -NH2·HQ, -NHZ·HQ, -N(Z)2·HQ, -N + (Z) 3X; wherein Y is selected from the group consisting of: H + NH4 + 、Li + 、Na + , K + Mg 2+ 、Al 3+ , Ca 2+ ;Q - Select from the following group: F - 、Cl - Br - , I - 、OH-、OAc - 、OTf - ,OTs - 、SO4 2- 、SO3 2- PO4 3- 、HPO4 2- 、H2PO4 - 、NO2 - 、NO3 - 、CO3 2- 、HCO3 - 、ClO4 - 、ClO3 - 、ClO2 - , ClO - 、CN - Z is selected from the following group: substituted or unsubstituted C1-C10 alkyl; said X - Select from the following group: F - 、Cl - Br - , I - OH - 、OAc - 、OTf- ,OTs - 、SO4 2- 、SO3 2- PO4 3- 、HPO4 2- 、H2PO4 - 、NO2 - 、NO3 - 、CO3 2- 、HCO3 - 、ClO4 - 、ClO3 - 、ClO2 - , ClO - 、CN - ;

[0011] Among them, R 6 The substituents can be located at One or more hydrogen atoms in the parent core structure are replaced, or the substituent is located on a heteroatom, R 6 Selected from the group consisting of H, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted 5-12 membered heterocycloalkyl or aryl, substituted or unsubstituted C6-C10 aryl, thiol (-S - or -SH), nitro (-NO2), cyano (-CN), halogen (-F or -Cl or -Br), -COOY, -SO3Y, -PO3Y, -NH2·HQ, -NHZ·HQ, -N(Z)2·HQ, -N + (Z) 3X; wherein Y is selected from the group consisting of: H + NH4 + 、Li + 、Na + , K + Mg 2+ 、Al 3+ , Ca 2+ ; Q-selected from the group consisting of: F - 、Cl - Br - , I - OH - 、OAc - 、OTf - ,OTs - 、SO4 2- 、SO3 2- PO4 3- 、HPO4 2- 、H2PO4 - 、NO2 - 、NO3 - 、CO3 2- 、HCO3- 、ClO4 - 、ClO3 - 、ClO2 - , ClO - 、CN - Z is selected from the following group: substituted or unsubstituted C1-C10 alkyl; said X - Select from the following group: F - 、Cl - Br - , I - OH - 、OAc - 、OTf - ,OTs - 、SO4 2- 、SO3 2- PO4 3- 、HPO4 2- 、H2PO4 - 、NO2 - 、NO3 - 、CO3 2- 、HCO3 - 、ClO4 - 、ClO3 - 、ClO2 - , ClO - 、CN - ;

[0012] x, y are selected from the following group: 0-20;

[0013] The novel iron-based complex is electrically neutral; the novel iron-based complex may or may not include one or more crystal waters;

[0014] M 2 is at least one charge-balancing ion, wherein the charge-balancing ion is a cation or anion; the cation is selected from the group consisting of: + NH4 + 、Li + 、Na + , K + Mg 2+ 、Al 3+ , Ca 2+ ; The anion is selected from the following group: F - 、Cl - Br - , I - OH - 、OAc - 、OTf - ,OTs - 、SO4 2- 、SO3 2-PO4 3- 、HPO4 2- 、H2PO4 - 、NO2 - 、NO3 - 、CO3 2- 、HCO3 - 、ClO4 - 、ClO3 - 、ClO2 - , ClO - 、CN - .

[0015] While adopting the above technical solutions, the present invention may also adopt or combine the following technical solutions:

[0016] As a preferred technical solution of the present invention: the substituted or unsubstituted 5-12 nitrogen-containing heteroaromatic ring is selected from the following groups:

[0017]

[0018]

[0019] As a preferred technical solution of the present invention: the substituted or unsubstituted 5-12 membered oxygen-containing heteroaromatic ring is selected from the following groups:

[0020]

[0021] As a preferred technical solution of the present invention: the substituted or unsubstituted 5-12 membered sulfur-containing heteroaromatic ring is selected from the following groups:

[0022]

[0023] As a preferred technical solution of the present invention: the carbon carbene structure is selected from the following groups:

[0024]

[0025] As a preferred technical solution of the present invention: is a substituted or unsubstituted 5-12-membered nitrogen-containing heteroaromatic ring, and the structural formula of the novel iron-based complex is shown below:

[0026]

[0027] The coordination form of the above nitrogen-containing heteroaromatic ring is as follows:

[0028]

[0029] As a preferred technical solution of the present invention: is a substituted or unsubstituted 5-12-membered oxygen-containing heteroaromatic ring, and the structural formula of the novel iron-based complex is shown below:

[0030]

[0031] The coordination form of the above oxygen-containing heteroaromatic ring is as follows:

[0032]

[0033] As a preferred technical solution of the present invention: is a substituted or unsubstituted 5-12 membered sulfur-containing heteroaromatic ring, and the structural formula of the novel iron-based complex is shown below:

[0034]

[0035] The coordination form of the above sulfur-containing heteroaromatic ring is as follows:

[0036]

[0037]

[0038] As a preferred technical solution of the present invention: It is a substituted or unsubstituted carbon carbene compound, and the structural formula of the novel iron-based complex is shown below:

[0039]

[0040] The coordination forms of the above nitrogen-containing heterocarbon carbenes are shown below:

[0041]

[0042] Another object of the present invention is to provide an application of the novel iron-based complex described above in electrochemical energy storage, for example, the use of the novel iron-based complex in the preparation of a liquid flow battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 For compound 1 1 H NMR spectrum.

[0044] Figure 2 For compound 2 1 H NMR spectrum.

[0045] Figure 3 For compound 3 1 H NMR spectrum.

[0046] Figure 4 For compound 4 1 H NMR spectrum.

[0047] Figure 5 For compound 5 1 H NMR spectrum.

[0048] Figure 6 For compound 6 1 H NMR spectrum.

[0049] Figure 7 For compound 7 1 H NMR spectrum.

[0050] Figure 8 For compound 8 1 H NMR spectrum.

[0051] Figure 9 For compound 9 1 H NMR spectrum.

[0052] Figure 10 For compound 10 1 H NMR spectrum.

[0053] Figure 11 For compound 11 1 H NMR spectrum.

[0054] Figure 12 For compound 12 1 H NMR spectrum.

[0055] Figure 13 Compound 13 1 H NMR spectrum.

[0056] Figure 14 Compound 14 1 H NMR spectrum.

[0057] Figure 15 Compound 15 1 H NMR spectrum.

[0058] Figure 16 For compound 16 1 H NMR spectrum.

[0059] Figure 17 Compound 17 1 H NMR spectrum.

[0060] Figure 18 For compound 18 1 H NMR spectrum.

[0061] Figure 19 Compound 19 1 H NMR spectrum.

[0062] Figure 20 Compound 20 1 H NMR spectrum.

[0063] Figure 21 For compound 21 1 H NMR spectrum.

[0064] Figure 22 Compound 22 1 H NMR spectrum.

[0065] Figure 23 Compound 23 1 H NMR spectrum.

[0066] Figure 24 Compound 24 1 H NMR spectrum.

[0067] Figure 25 Compound 25 1 H NMR spectrum.

[0068] Figure 26 This is the cyclic voltammogram of compound 1 in 1.0 M NaCl solution.

[0069] Figure 27 This is the cyclic voltammogram of compound 2 in 1.0 M NaCl solution.

[0070] Figure 28 This is the cyclic voltammogram of compound 3 in 1.0 M NaCl solution.

[0071] Figure 29 This is the cyclic voltammogram of compound 4 in 1.0 M NaCl solution.

[0072] Figure 30 This is the cyclic voltammogram of compound 5 in 1.0 M NaCl solution.

[0073] Figure 31 This is the cyclic voltammogram of compound 6 in 1.0 M NaCl solution.

[0074] Figure 32 This is the cyclic voltammogram of compound 7 in 1.0 M NaCl solution.

[0075] Figure 33 This is the cyclic voltammogram of compound 8 in 1.0 M NaCl solution.

[0076] Figure 34 This is the cyclic voltammogram of compound 10 in 1.0 M KCl solution.

[0077] Figure 35This is the cyclic voltammogram of compound 11 in 1.0 M KCl solution.

[0078] Figure 36 This is the cyclic voltammogram of compound 12 in 1.0 M KCl solution.

[0079] Figure 37 This is the cyclic voltammogram of compound 13 in 1.0 M KCl solution.

[0080] Figure 38 This is the cyclic voltammogram of compound 14 in 1.0 M KCl solution.

[0081] Figure 39 This is the cyclic voltammogram of compound 15 in 1.0 M KCl solution.

[0082] Figure 40 This is the cyclic voltammogram of compound 16 in 1.0 M KCl solution.

[0083] Figure 41 This is the cyclic voltammogram of compound 17 in 1.0 M KCl solution.

[0084] Figure 42 This is the cyclic voltammogram of compound 18 in 1.0 M KCl solution.

[0085] Figure 43 This is the cyclic voltammogram of compound 19 in 1.0 M KCl solution.

[0086] Figure 44 This is the cyclic voltammogram of compound 20 in 1.0 M KCl solution.

[0087] Figure 45 This is the cyclic voltammogram of compound 21 in 1.0 M KCl solution.

[0088] Figure 46 This is the cyclic voltammogram of compound 22 in 1.0 M KCl solution.

[0089] Figure 47 This is the cyclic voltammogram of compound 23 in 1.0 M KCl solution.

[0090] Figure 48 This is the cyclic voltammogram of compound 24 in 1.0 M KCl solution.

[0091] Figure 49 This is the cyclic voltammogram of compound 25 in 1.0 M KCl solution.

[0092] Figure 50 Schematic diagram of a flow battery.

[0093] Figure 51 This is a battery cycle test diagram of compound 1 as the positive electrode of the flow battery.

[0094] Figure 52 This is the current cycling test diagram of compound 4 as the positive electrode of the flow battery.

[0095] Figure 53 This is the current cycling test diagram of compound 5 as the positive electrode of the flow battery.

[0096] Figure 54 This is the current cycling test diagram of compound 6 as the positive electrode of the flow battery.

[0097] Figure 55 The long-cycle charge-discharge capacity change and coulombic efficiency diagram of compound 6 as the positive electrode of liquid flow battery.

[0098] Figure 56 This is the current cycling test diagram of compound 7 as the positive electrode of the flow battery.

[0099] Figure 57 This is the current cycling test diagram of compound 8 as the positive electrode of the flow battery.

[0100] Figure 58 This is the current cycling test diagram of compound 10 as the positive electrode of the flow battery.

[0101] Figure 59 The long-cycle charge-discharge capacity change and coulombic efficiency diagram of compound 10 as the positive electrode of liquid flow battery.

[0102] Figure 60 This is the current cycling test diagram of compound 14 as the positive electrode of the flow battery.

[0103] Figure 61 The long-cycle charge-discharge capacity change and coulombic efficiency diagram of compound 14 as the positive electrode of liquid flow battery.

[0104] Figure 62 This is the current cycling test diagram of compound 15 as the positive electrode of the flow battery.

[0105] Figure 63 The long-cycle charge-discharge capacity change and coulombic efficiency diagram of compound 15 as the positive electrode of liquid flow battery.

[0106] Figure 64 This is the current cycling test diagram of compound 16 as the positive electrode of the flow battery.

[0107] Figure 65 The long-cycle charge-discharge capacity change and coulombic efficiency diagram of compound 16 as the positive electrode of liquid flow battery.

[0108] Figure 66This is the current cycling test diagram of compound 17 as the positive electrode of the flow battery.

[0109] Figure 67 The long-cycle charge-discharge capacity change and coulombic efficiency diagram of compound 17 as the positive electrode of liquid flow battery.

[0110] Figure 68 This is the current cycling test diagram of compound 18 as the positive electrode of the flow battery.

[0111] Figure 69 The long-cycle charge-discharge capacity change and coulombic efficiency diagram of compound 18 as the positive electrode of liquid flow battery.

[0112] Figure 70 This is the current cycling test diagram of compound 10 as the positive electrode of the flow battery.

[0113] Figure 71 The long-cycle charge-discharge capacity change and coulombic efficiency diagram of compound 10 as the positive electrode of liquid flow battery.

[0114] Figure 72 This is the current cycling test diagram of compound 19 as the positive electrode of the liquid flow battery.

[0115] Figure 73 The long-cycle charge-discharge capacity change and coulombic efficiency diagram of compound 19 as the positive electrode of liquid flow battery.

[0116] Figure 74 This is the current cycling test diagram of compound 20 as the positive electrode of the flow battery.

[0117] Figure 75 The long-cycle charge-discharge capacity change and coulombic efficiency diagram of compound 20 as the positive electrode of liquid flow battery.

[0118] Figure 76 This is the current cycling test diagram of compound 22 as the positive electrode of the liquid flow battery.

[0119] Figure 77 The long-cycle charge-discharge capacity change and coulombic efficiency diagram of compound 22 as the positive electrode of liquid flow battery. DETAILED DESCRIPTION

[0120] The present invention will be further described in detail with reference to the accompanying drawings and specific embodiments.

[0121] Among the compounds described above, the following compounds are selected as examples. The compounds have the following structures, and other corresponding counterions can be obtained by ion exchange.

[0122]

[0123] In the following examples, the experimental methods without specific conditions are generally based on conventional conditions or the conditions recommended by the manufacturer. Unless otherwise specified, percentages and parts are calculated by weight.

[0124] 1. Synthesis Experiment Example

[0125] Example 1 (Compound 1)

[0126]

[0127] Weigh 2.0g of pyrazine and mix it with 10.0mL of iodomethane, react at room temperature in the dark for 7 days to obtain a yellow precipitate. The obtained solid was recrystallized from ethanol to obtain compound 22; 6.0g of sodium nitroprusside was mixed with 30.0mL of ammonia water, stirred for 6.0h at room temperature in the dark, 6.0g of NaI was added to precipitate a yellow solid, and 100.0mL of ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 0.7g (5.0eq) of compound 22 and 0.2g (1.0eq) of compound S2 were dissolved in 1.0mL of deionized water, stirred at 0℃ for 30.0min, and then 1.0g of NaI was added, and 30.0mL of ethanol was added to precipitate a solid, which was filtered to obtain 0.7g of compound 1. 1 HNMR images Figure 1 shown.

[0128] Example 2 (Compound 2)

[0129]

[0130] 6.0 g of sodium nitroprusside was mixed with 30.0 mL of ammonia water, stirred for 6.0 h at room temperature in the dark, 6.0 g of NaI was added to precipitate a yellow solid, and 100.0 mL of ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 40.0 mg (1.0 eq) of pyridine and 326.0 mg (2.0 eq) of compound S2 were dissolved in 1.0 mL of deionized water, respectively, and stirred at room temperature for 30.0 min. Then 1.0 g of NaI was added, and 30.0 mL of ethanol was added to precipitate a solid, which was filtered to obtain 170.0 mg of compound 2. 1 H NMR spectrum Figure 2 shown.

[0131] Example 3 (Compound 3)

[0132]

[0133] 6.0 g of sodium nitroprusside was mixed with 30.0 mL of ammonia water, stirred for 6.0 h at room temperature in the dark, 6.0 g of NaI was added to precipitate a yellow solid, and 100.0 mL of ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 47.6 mg (1.0 eq) of 3-hydroxypyridine and 326.0 mg (2.0 eq) of compound S2 were dissolved in 1.0 mL of deionized water, stirred at room temperature for 30.0 min, and then 1.0 g of NaI was added, and 30.0 mL of ethanol was added to precipitate a solid, which was filtered to obtain 170.0 mg of compound 3. 1 H NMR spectrum Figure 3 shown.

[0134] Example 4 (Compound 4)

[0135]

[0136] 6.0 g of sodium nitroprusside was mixed with 30.0 mL of ammonia water, stirred for 6.0 h at room temperature in the dark, 6.0 g of NaI was added to precipitate a yellow solid, and 100.0 mL of ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 79.6 mg (1.0 eq) of 3-hydroxypyridine and 326.0 mg (2.0 eq) of compound S2 were dissolved in 1.0 mL of deionized water, stirred at room temperature for 30.0 min, and then 1.0 g of NaI was added, and 30.0 mL of ethanol was added to precipitate a solid, which was filtered to obtain 196.0 mg of compound 4. 1 H NMR spectrum Figure 4 shown.

[0137] Example 5 (Compound 5)

[0138]

[0139] 6.0 g of sodium nitroprusside was mixed with 30.0 mL of ammonia water, stirred for 6.0 h at room temperature in the dark, 6.0 g of NaI was added to precipitate a yellow solid, and 100.0 mL of ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 61.5 mg (1.0 eq) of 4-carboxylic acid pyridine was dissolved in 5.0 mL of deionized water, and 326.0 mg (2.0 eq) of compound S2 was dissolved in 1.0 mL of deionized water. The two solutions were mixed and stirred at room temperature for 30.0 min, and then 1.0 g of NaI was added, and 30.0 mL of ethanol was added to precipitate a solid, which was filtered to obtain 227.0 mg of compound 5. 1 HNMR images Figure 5 shown.

[0140] Example 6 (Compound 6)

[0141]

[0142] 6.0 g of sodium nitroprusside was mixed with 30.0 mL of ammonia water, stirred for 6.0 h at room temperature in the dark, 6.0 g of NaI was added to precipitate a yellow solid, and 100 mL of ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 61.5 mg (1.0 eq) of 3-carboxylic acid pyridine was dissolved in 5.0 mL of deionized water, and 326.0 mg (2.0 eq) of compound S2 was dissolved in 1.0 mL of deionized water. The two solutions were mixed and stirred at room temperature for 30.0 min, and then 1.0 g of NaI was added, and 30.0 mL of ethanol was added to precipitate a solid, which was filtered to obtain 260.0 mg of compound 6. 1 H NMR spectrum Figure 6 shown.

[0143] Example 7 (Compound 7)

[0144]

[0145] 6.0 g of sodium nitroprusside was mixed with 30.0 mL of ammonia water, stirred for 6.0 h at room temperature in the dark, 6.0 g of NaI was added to precipitate a yellow solid, and 100.0 mL of ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 84.0 mg (1.0 eq) of 3-nitroisonicotinic acid was dissolved in 5.0 mL of deionized water, and 326.0 mg (2.0 eq) of compound S2 was dissolved in 1.0 mL of deionized water. The two solutions were mixed and stirred at room temperature for 30.0 min, and then 1.0 g of NaI was added, and 30.0 mL of ethanol was added to precipitate a solid, which was filtered to obtain 199.0 mg of compound 7. 1 HNMR images Figure 7 shown.

[0146] Example 8 (Compound 8)

[0147]

[0148] Weigh 0.9 g of 4,4'bipyridine and 1.4 g of trimethylammonium bromide, reflux in 5.0 mL of acetonitrile for 12.0 h under nitrogen protection to obtain a pure white precipitate, which was filtered and washed with dichloromethane to obtain a pure white solid compound S3. 6.0 g of sodium nitroprusside was mixed with 30.0 mL of ammonia water, stirred at room temperature in the dark for 6.0 h, 6.0 g of NaI was added to precipitate a yellow solid, and 100.0 mL of ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 83.0 mg (2.0 eq) of compound S3 and 326.0 mg (1.0 eq) of compound S2 were dissolved in 1.0 mL of deionized water, respectively, and stirred at room temperature for 30.0 min. Then 1.0 g of NaI was added, and 30.0 mL of ethanol was added to precipitate a solid, which was filtered to obtain 0.7 g of compound 8. 1 H NMR spectrum Figure 8 shown.

[0149] Example 9 (Compound 9)

[0150]

[0151] Weigh 1.6g N-methylimidazole and 1.8g iodomethane, add 15.0mL acetone and seal the reaction at 70.0℃ for 12.0h to produce a yellow solid, which is directly spin-dried to obtain compound S4. 6.0g sodium nitroprusside is mixed with 30.0mL ammonia water, stirred at room temperature in the dark for 6.0h, 6.0g NaI is added to precipitate a yellow solid, and 100.0mL ethanol is added to further precipitate more solid, which is collected by filtration to obtain compound S2. 223.9mg (1.0eq) of compound S4 is mixed with 5.0mL THF under nitrogen, cooled to -78.0℃, 1.87mL t-BuLi is added, and stirring is continued for a while, then placed at room temperature and stirred. After 1h, 326.0mg (1.0eq) of compound S2 is added, and stirring is continued at room temperature under nitrogen protection for 12.0h. Ethanol is added to quench the reaction to obtain 240.0mg of compound 9. 1 H NMR spectrum Figure 9 shown.

[0152] Example 10 (Compound 10)

[0153] Weigh 2.0g of 2-pyrazinecarboxylic acid and dissolve it completely in deionized water with sodium hydroxide, heat and distill to remove excess water, filter before the solution is completely evaporated, wash with ethanol to obtain pure 2-pyrazinecarboxylic acid sodium salt. Mix 6.0g of sodium nitroprusside with 30.0mL of ammonia water, stir for 6.0h at room temperature in the dark, add 6.0g of NaI to precipitate a yellow solid, then add 100.0mL of ethanol to further precipitate more solid, filter and collect to obtain compound S2. Dissolve 0.2g (1.5eq) of 2-pyrazinecarboxylic acid sodium salt in 3.0mL of water, and dissolve 0.3g (1.0eq) of compound S2 in 1.0mL of deionized water and then slowly drip into the above aqueous solution. Stir at room temperature for 3.0h, then add 30.0mL of ethanol to precipitate a solid, filter to obtain 0.4g of compound 10, and compound 10 1 H NMR spectrum Figure 10 shown.

[0154]

[0155] Example 11 (Compound 11)

[0156]

[0157] Weigh 2.0g of pyrazinedicarboxylic acid and dissolve it completely with sodium hydroxide in deionized water. Remove excess water by heating and distilling. Filter before the solution is completely evaporated to dryness, wash with ethanol to obtain pure pyrazinedicarboxylic acid sodium salt. Mix 6.0g of sodium nitroprusside with 30mL of ammonia water, stir for 6.0h at room temperature in the dark, add 6.0g of NaI to precipitate a yellow solid, then add 100.0mL of ethanol to further precipitate more solid, filter and collect to obtain compound S2. Dissolve 0.2g (1.5eq) of pyrazinedicarboxylic acid sodium salt in 3.0mL of water, and dissolve 0.32g (1.0eq) of compound S2 in 1.0mL of deionized water and then slowly drip into the above aqueous solution. Stir at room temperature for 3.0h, then add 30.0mL of ethanol to precipitate a solid, filter and obtain 0.4g of compound 11. Compound 11 1 HNMR images Figure 11 shown.

[0158] Example 12 (Compound 12)

[0159]

[0160] 6.0g of sodium nitroprusside was mixed with 30.0mL of ammonia water, stirred at room temperature in the dark for 6.0h, 6g of NaI was added to precipitate a yellow solid, and 100.0mL of ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 0.61g (5eq) of DMAP was dissolved in 3.0mL of deionized water, and 326.0mg (1.0eq) of compound S2 was dissolved in 1.0mL of deionized water. The two solutions were mixed and stirred at room temperature for 30.0min, and then 1.0g of NaI was added, and then 30.0mL of ethanol was added to precipitate a solid, which was filtered to obtain 391.0mg of compound 12. 1 HNMR images Figure 12 shown.

[0161] Example 13 (Compound 13)

[0162]

[0163] 6.0g of sodium nitroprusside was mixed with 30.0mL of ammonia water, stirred for 6.0h at room temperature in the dark, 6.0g of NaI was added to precipitate a yellow solid, and 100mL of ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 0.63g (5eq) of N-methylimidazolecarboxylic acid was dissolved in 3.0mL of deionized water, and 325.97mg (1.0eq) of compound S2 was dissolved in 1.0mL of deionized water. The two solutions were mixed and stirred at room temperature for 30.0min, and then 1.0g of NaI was added, and 30.0mL of ethanol was added to precipitate a solid, which was filtered to obtain 401.0mg of compound 13. 1 HNMR images Figure 13 shown.

[0164] Example 14 (Compound 14)

[0165]

[0166] 6.0 g of sodium nitroprusside was mixed with 30.0 mL of ammonia water, stirred for 6.0 h at room temperature in the dark, 100.0 mL of ethanol was added to precipitate the solid, which was collected by filtration to obtain compound S2. 326.0 mg (1.0 eq) of compound S2 was dissolved in 2.0 mL of deionized water, and 550.0 mg (5.0 eq) of 2-hydroxymethylpyrazine was added. The mixture was stirred at room temperature for 30.0 min and vacuum dried. 50.0 mL of ethyl acetate was beaten at 60.0 ° C for 3.0 h, filtered, and vacuum dried to obtain 360.0 mg of compound 14. 1 H NMR spectrum Figure 14 shown.

[0167] Example 15 (Compound 15)

[0168]

[0169] 1.1 g of 2-hydroxymethylpyrazine was dissolved in 10.0 mL of DCM at 0°C, and 1.4 mL of thionyl chloride was added dropwise. The mixture was stirred for 3.0 h, filtered, and washed with 50.0 mL of ether to obtain 1.0 g of 2-chloromethylpyrazine with a yield of nearly 80.0%. 0.26 g of 2-chloromethylpyrazine was dissolved in 3.0 mL of DMF, and 10.0 mL of a tetrahydrofuran solution of trimethylamine was added. The mixture was stirred at 50.0°C for 12.0 h. After the reaction, 50.0 mL of ether was added, filtered, washed with 50.0 mL of ether, and dried in vacuo to obtain 0.3 g of compound S5 with a yield of 80.0%. 6.0 g of sodium nitroprusside was mixed with 30.0 mL of ammonia water, stirred for 6.0 h at room temperature in the dark, 100.0 mL of ethanol was added to precipitate the solid, and the solid was collected by filtration to obtain compound S2. 326.0 mg (1.0 eq) of compound S2 was dissolved in 2.0 mL of deionized water, and 939.5 mg (5.0 eq) of compound S5 was added. The mixture was stirred at room temperature for 30.0 min, vacuum-dried, 50.0 mL of ethanol was beaten at 60.0 ° C for 3.0 h, filtered, and vacuum-dried to obtain 377.7 mg of compound 15. 1 HNMR images Figure 15 shown.

[0170] Example 16 (Compound 16)

[0171]

[0172] 0.8 g of 2-bromopyrazine was reacted with 25.0 mL of trimethylamine in tetrahydrofuran at 50.0°C for 12.0 h. After the reaction, the mixture was filtered, washed with 50.0 mL of ether, and dried under vacuum to obtain 0.3 g of compound S6 with a yield of 31%. 6.0 g of sodium nitroprusside was mixed with 30.0 mL of ammonia water and stirred at room temperature in the dark for 6.0 h. 100.0 mL of ethanol was added to precipitate a solid, which was collected by filtration to obtain compound S2. 326.0 mg (1.0 eq) of compound S2 was dissolved in

[0173] 1.1 g (5.0 eq) of compound S6 was added to 2.0 mL of deionized water, stirred at room temperature for 30.0 min, freeze-dried, washed with 50.0 mL of ethanol, filtered, and dried under vacuum at room temperature to obtain 458.1.0 mg of compound 16. 1 H NMR spectrum Figure 16 shown.

[0174] Example 17 (Compound 17)

[0175]

[0176] 2.1g 2-cyanopyrimidine was added with 1.9g NaOH and 5.0mL water, stirred at 0℃ for 10.0min, then stirred at 55.0℃ for 2.0h. After the reaction, it was dried under vacuum and washed with 50.0mL ethanol to obtain 2.8g compound S7 with a yield of 96%. 6.0g sodium nitroprusside was mixed with 30.0mL ammonia water and stirred at room temperature in the dark for 6.0h. 100.0mL ethanol was added to precipitate the solid, which was collected by filtration to obtain compound S2. 326.0mg (1.0eq) of compound S2 was dissolved in 2.0mL deionized water, and 730.0mg (5.0eq) of compound S7 was added. The mixture was stirred at room temperature for 30.0min, dried under vacuum, slurried with 50.0mL ethanol at 60.0℃ for 3.0h, filtered, and dried under vacuum to obtain 349.6mg of compound 17. 1 HNMR images Figure 17 shown.

[0177] Example 18 (Compound 18)

[0178] 2.2g 2-chloropyrimidine was reacted with 25.0mL trimethylamine tetrahydrofuran solution at room temperature for 12.0h. After the reaction, the mixture was filtered, washed with 50.0mL ether, and dried under vacuum to obtain 2.5g compound S8 with a yield of 90.6%. 6.0g sodium nitroprusside was mixed with 30.0mL ammonia water, stirred at room temperature for 6.0h in the dark, and 100.0mL ethanol was added to precipitate the solid, which was collected by filtration to obtain compound S2. 326.0mg (1.0eq) of compound S2 was dissolved in 2.0mL deionized water, and 690.0mg (5.0eq) of compound S8 was added. The mixture was stirred at room temperature for 30.0min. After the reaction, the mixture was dried under vacuum and washed with 50.0mL ethanol to obtain 3S2.8mg of compound 18. 1 HNMR images Figure 18 shown.

[0179]

[0180] Example 19 (Compound 19)

[0181]

[0182] 6.0g of sodium nitroprusside was mixed with 30.0mL of ammonia water, stirred at room temperature in the dark for 6.0h, 6.0g of NaI was added to precipitate a yellow solid, and 100mL of ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 0.63g (5eq) of 2-cyanopyrazine was dissolved in 3.0mL of deionized water, and 325.97mg (1.0eq) of compound S2 was dissolved in 1.0mL of deionized water. The two solutions were mixed and stirred at room temperature for 30.0min, and then 1.0g of NaI was added, and 30.0mL of ethanol was added to precipitate a solid, which was filtered to obtain 368.0mg of compound 19. 1 H NMR spectrum Figure 19 shown.

[0183] Example 20 (Compound 20)

[0184]

[0185] 6.0g sodium nitroprusside was mixed with 30.0mL ammonia water, stirred for 6.0h at room temperature in the dark, 6.0g NaI was added to precipitate a yellow solid, and 100mL ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 2.0g 2-fluoropyrazine and 3.9g sodium sulfite were dissolved in 20mL water, reacted at 150°C for 12.0h, and vacuum dried before use in the next step. Compound S2 was dissolved in 2.0mL deionized water, and 910.0mg (5.0eq) compound S9 was added, stirred at room temperature for 30.0min, and 50.0mL ethanol was added to precipitate a solid after the reaction was completed. It was washed with 50.0mL ethanol to obtain 3S2.8mg compound 20, compound 20 1 H NMR spectrum Figure 20 shown.

[0186] Example 21 (Compound 21)

[0187]

[0188] 6.0g of sodium nitroprusside was mixed with 30.0mL of ammonia water, stirred for 6.0h at room temperature in the dark, 6.0g of NaI was added to precipitate a yellow solid, and 100mL of ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 0.47g (5eq) of 2-methylpyrazine was dissolved in 3.0mL of deionized water, and 325.97mg (1.0eq) of compound S2 was dissolved in 1.0mL of deionized water. The two solutions were mixed and stirred at room temperature for 30.0min, and then 1.0g of NaI was added, and 30.0mL of ethanol was added to precipitate a solid, which was filtered to obtain 368.0mg of compound 21. 1 H NMR spectrum Figure 21 shown.

[0189] Example 22 (Compound 22)

[0190]

[0191] 6.0g of sodium nitroprusside was mixed with 30.0mL of ammonia water, stirred for 6.0h at room temperature in the dark, 6.0g of NaI was added to precipitate a yellow solid, and 100mL of ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 0.47g (5eq) of 2-formamide pyrazine was dissolved in 3.0mL of deionized water, and 325.97mg (1.0eq) of compound S2 was dissolved in 1.0mL of deionized water. The two solutions were mixed and stirred at room temperature for 30.0min, and then 1.0g of NaI was added, and 30.0mL of ethanol was added to precipitate a solid, which was filtered to obtain 349.0mg of compound 22. 1 HNMR images Figure 22 shown.

[0192] Example 23 (Compound 23)

[0193]

[0194] 6.0g of sodium nitroprusside was mixed with 30.0mL of ammonia water, stirred for 6.0h at room temperature in the dark, 6.0g of NaI was added to precipitate a yellow solid, and 100mL of ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 0.16g (2eq) of pyrimidine was dissolved in 3.0mL of deionized water, and 325.97mg (1.0eq) of compound S2 was dissolved in 1.0mL of deionized water. The two solutions were mixed and stirred at room temperature for 30.0min, and then 1.0g of NaI was added, and 30.0mL of ethanol was added to precipitate a solid, which was filtered to obtain 355.0mg of compound 23. 1 HNMR images Figure 23 shown.

[0195] Example 24 (Compound 24)

[0196]

[0197] 6.0g of sodium nitroprusside was mixed with 30.0mL of ammonia water, stirred for 6.0h at room temperature in the dark, 6.0g of NaI was added to precipitate a yellow solid, and 100mL of ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 0.16g (2eq) of triazine was dissolved in 3.0mL of deionized water, and 325.97mg (1.0eq) of compound S2 was dissolved in 1.0mL of deionized water. The two solutions were mixed and stirred at room temperature for 30.0min, and then 1.0g of NaI was added, and 30.0mL of ethanol was added to precipitate a solid, which was filtered to obtain 355.0mg of compound 24. 1 H NMR spectrum Figure 24 shown.

[0198] Example 25 (Compound 25)

[0199]

[0200] 6.0g of sodium nitroprusside was mixed with 30.0mL of ammonia water, stirred for 6.0h at room temperature in the dark, 6.0g of NaI was added to precipitate a yellow solid, and 100mL of ethanol was added to further precipitate more solid, which was collected by filtration to obtain compound S2. 0.19g (2eq) of 2-fluoropyrazine was dissolved in 3.0mL of deionized water, and 325.97mg (1.0eq) of compound S2 was dissolved in 1.0mL of deionized water. The two solutions were mixed and stirred at room temperature for 30.0min, and then 1.0g of NaI was added, and 30.0mL of ethanol was added to precipitate a solid, which was filtered to obtain 329.0mg of compound 25. 1 H NMR spectrum Figure 25 shown.

[0201] 2. Test Experiment Example

[0202] Example 1: Cyclic voltammetry test (Compound 1)

[0203] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum wire electrode. The voltage sweep range was -0.5 V to 1.2 V at a scan rate of 20.0 mV / s. The concentration of compound 1 was 5.0 mM.

[0204] The cyclic voltammogram of the test compound in 1.0 M NaCl solution is shown in Figure 4. Figure 26 The results showed that the compound can exhibit two pairs of reversible redox peaks under neutral (NaCl) conditions, and the low potential E 1 / 2 =-0.65V, high potential E 1 / 2 =0.71 V, and the compound has a relatively high redox potential when used as a positive electrode.

[0205] Example 2: Cyclic Voltammetry Test (Compound 2)

[0206] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum wire electrode. The voltage sweep range was 0 V to 0.6 V at a scan rate of 20.0 mV / s. The concentration of compound 2 was 5.0 mM.

[0207] The cyclic voltammogram of the test compound in 1.0 M NaCl solution is shown in Figure 4. Figure 27 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (NaCl) conditions, E 1 / 2 =0.33V.

[0208] Example 3: Cyclic voltammetry test (Compound 3)

[0209] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum wire electrode. The voltage sweep range was 0 V to 0.6 V at a scan rate of 20.0 mV / s. The concentration of compound 3 was 5.0 mM.

[0210] The cyclic voltammogram of the test compound in 1.0 M NaCl solution is shown in Figure 4. Figure 28 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (NaCl) conditions, E 1 / 2 =0.36V.

[0211] Example 4: Cyclic voltammetry test (Compound 4)

[0212] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum wire electrode. The voltage sweep range was 0 V to 0.6 V at a scan rate of 20.0 mV / s. The concentration of compound 4 was 5.0 mM.

[0213] The cyclic voltammogram of the test compound in 1.0 M NaCl solution is shown in Figure 4. Figure 29 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (NaCl) conditions, E 1 / 2 =0.42V, the concentration of compound 4 is 5.0 mM.

[0214] Example 5: Cyclic voltammetry test (Compound 5)

[0215] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum wire electrode. The voltage sweep range was 0 V to 0.6 V at a scan rate of 20.0 mV / s. The concentration of compound 5 was 5.0 mM.

[0216] The cyclic voltammogram of the test compound in 1.0 M NaCl solution is shown in Figure 4. Figure 30 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (NaCl) conditions, E 1 / 2 =0.39V.

[0217] Example 6: Cyclic voltammetry test (Compound 6)

[0218] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum wire electrode. The voltage sweep range was 0 V to 0.6 V at a scan rate of 20.0 mV / s. The concentration of compound 6 was 5.0 mM.

[0219] The cyclic voltammogram of the test compound in 1.0 M NaCl solution is shown in Figure 4. Figure 31 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (NaCl) conditions, E 1 / 2 =0.40V.

[0220] Example 7: Cyclic voltammetry test (Compound 7)

[0221] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum wire electrode. The voltage sweep range was 0 V to 0.6 V at a scan rate of 20.0 mV / s. The concentration of compound 7 was 5.0 mM.

[0222] The cyclic voltammogram of the test compound in 1.0 M NaCl solution is shown in Figure 4. Figure 32 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (NaCl) conditions, E 1 / 2 =0.44V.

[0223] Example 8: Cyclic voltammetry test (Compound 8)

[0224] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum wire electrode. The voltage sweep range was -0.6 V to 1.2 V at a scan rate of 20.0 mV / s. The concentration of compound 8 was 5.0 mM.

[0225] The cyclic voltammogram of the test compound in 1.0 M NaCl solution is shown in Figure 4. Figure 33 The results showed that the compound can exhibit two pairs of reversible redox peaks under neutral (NaCl) conditions, and the low potential E 1 / 2 =-0.73V, high potential E 1 / 2 =0.66 V, and the compound has a relatively high redox potential when used as a positive electrode.

[0226] Example 9: Cyclic voltammetry test (Compound 10)

[0227] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum wire electrode. The voltage sweep range was 0.3 V to 0.9 V at a scan rate of 20.0 mV / s. The concentration of compound 10 was 5.0 mM.

[0228] The cyclic voltammogram of the test compound in 1.0 M KCl solution is shown in Figure 4. Figure 34 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (KCl) conditions, E 1 / 2 =0.60V.

[0229] Example 10: Cyclic voltammetry test (Compound 11)

[0230] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum wire electrode. The voltage sweep range was 0.1 V to 0.5 V at a scan rate of 20.0 mV / s. The concentration of compound 11 was 5.0 mM.

[0231] The cyclic voltammogram of the test compound in 1.0 M KCl solution is shown in Figure 4. Figure 35 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (KCl) conditions, E 1 / 2 =0.35V.

[0232] Example 11: Cyclic voltammetry test (Compound 12)

[0233] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum wire electrode. The voltage sweep range was 0.1 V to 0.5 V at a scan rate of 20.0 mV / s. The concentration of compound 12 was 10 mM.

[0234] The cyclic voltammogram of the test compound in 1.0 M KCl solution is shown in Figure 4. Figure 36 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (KCl) conditions, E 1 / 2 =0.35V.

[0235] Example 12: Cyclic voltammetry test (Compound 13)

[0236] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum wire electrode. The voltage sweep range was 0.1 V to 0.5 V at a scan rate of 20.0 mV / s. The concentration of compound 13 was 10 mM.

[0237] The cyclic voltammogram of the test compound in 1.0 M KCl solution is shown in Figure 4. Figure 37 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (KCl) conditions, E 1 / 2 =0.36V.

[0238] Example 13: Cyclic voltammetry test (Compound 14)

[0239] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum mesh electrode. The voltage sweep range was 0 V to 1.0 V at a scan rate of 50.0 mV / s. The concentration of compound 14 was 5.0 mM.

[0240] The cyclic voltammogram of the test compound in 1.0 M KCl solution is shown in Figure 4. Figure 38 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (KCl) conditions, E 1 / 2 =0.6V.

[0241] Example 14: Cyclic voltammetry test (Compound 15)

[0242] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum mesh electrode. The voltage sweep range was 0 V to 0.7 V at a scan rate of 50.0 mV / s. The concentration of compound 15 was 5.0 mM.

[0243] The cyclic voltammogram of the test compound in 1.0 M KCl solution is shown in Figure 4. Figure 39 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (KCl) conditions, E 1 / 2 =0.66V.

[0244] Example 15: Cyclic voltammetry test (Compound 16)

[0245] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum mesh electrode. The voltage sweep range was 0 V to 1.0 V at a scan rate of 50.0 mV / s. The concentration of compound 16 was 5.0 mM.

[0246] The cyclic voltammogram of the test compound in 1.0 M KCl solution is shown in Figure 4. Figure 40 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (KCl) conditions, E 1 / 2 =0.70V.

[0247] Example 16: Cyclic voltammetry test (Compound 17)

[0248] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum mesh electrode. The voltage sweep range was -1.0 V to 1.0 V at a scan rate of 50.0 mV / s. The concentration of compound 17 was 5.0 mM.

[0249] The cyclic voltammogram of the test compound in 1.0 M KCl solution is shown in Figure 4. Figure 41 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (KCl) conditions, E 1 / 2 =0.43V.

[0250] Example 17: Cyclic voltammetry test (Compound 18)

[0251] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum mesh electrode. The voltage sweep range was 0 V to 0.6 V at a scan rate of 50.0 mV / s. The concentration of compound 18 was 5.0 mM.

[0252] The cyclic voltammogram of the test compound in 1.0 M KCl solution is shown in Figure 4. Figure 42 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (KCl) conditions, E 1 / 2 =0.47V.

[0253] Example 18: Cyclic voltammetry test (Compound 19)

[0254] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum mesh electrode. The voltage sweep range was 0 V to 1.0 V at a scan rate of 50.0 mV / s. The concentration of compound 19 was 5.0 mM.

[0255] The cyclic voltammogram of the test compound in 1.0 M KCl solution is shown in Figure 4. Figure 43 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (KCl) conditions, E 1 / 2 =0.67V.

[0256] Example 19: Cyclic voltammetry test (Compound 20)

[0257] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum mesh electrode. The voltage sweep range was 0 V to 1.0 V at a scan rate of 50.0 mV / s. The concentration of compound 20 was 5.0 mM.

[0258] The cyclic voltammogram of the test compound in 1.0 M KCl solution is shown in Figure 4. Figure 44 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (KCl) conditions, E 1 / 2 =0.66V.

[0259] Example 20: Cyclic voltammetry test (Compound 21)

[0260] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum mesh electrode. The voltage sweep range was 0 V to 1.0 V at a scan rate of 50.0 mV / s. The concentration of compound 21 was 5.0 mM.

[0261] The cyclic voltammogram of the test compound in 1.0 M KCl solution is shown in Figure 4. Figure 45 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (KCl) conditions, E 1 / 2 =0.58V.

[0262] Example 21: Cyclic voltammetry test (Compound 22)

[0263] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum mesh electrode. The voltage sweep range was 0 V to 1.0 V at a scan rate of 50.0 mV / s. The concentration of compound 22 was 5.0 mM.

[0264] The cyclic voltammogram of the test compound in 1.0 M KCl solution is shown in Figure 4. Figure 46 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (KCl) conditions, E 1 / 2 =0.62V.

[0265] Example 22: Cyclic voltammetry test (Compound 23)

[0266] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum mesh electrode. The voltage sweep range was 0 V to 1.0 V at a scan rate of 50.0 mV / s. The concentration of compound 23 was 5.0 mM.

[0267] The cyclic voltammogram of the test compound in 1.0 M KCl solution is shown in Figure 4. Figure 47 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (KCl) conditions, E 1 / 2 =0.57V.

[0268] Example 23: Cyclic voltammetry test (Compound 24)

[0269] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum mesh electrode. The voltage sweep range was 0 V to 1.0 V at a scan rate of 50.0 mV / s. The concentration of compound 24 was 5.0 mM.

[0270] The cyclic voltammogram of the test compound in 1.0 M KCl solution is shown in Figure 4. Figure 48 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (KCl) conditions, E 1 / 2 =0.66V.

[0271] Example 24: Cyclic voltammetry test (Compound 25)

[0272] Cyclic voltammetry was performed using a three-electrode system. The working electrode was a 5.0 mM glassy carbon electrode, the reference electrode was aqueous Ag / AgCl, and the counter electrode was a platinum mesh electrode. The voltage sweep range was 0 V to 1.0 V at a scan rate of 50.0 mV / s. The concentration of compound 25 was 5.0 mM.

[0273] The cyclic voltammogram of the test compound in 1.0 M KCl solution is shown in Figure 4. Figure 49 The results showed that the compound can exhibit a pair of reversible redox peaks under neutral (KCl) conditions, E1 / 2 =0.64V.

[0274] Example 25: Current Cycling Test (Compound 1)

[0275] The main parameters and schematic diagram of the flow battery device are as follows: Figure 50 As shown, the current cycling test was performed using an electrochemical workstation for constant current charge and discharge cycle testing. The synthesized compound was used to assemble a battery, using an ion selective permeable membrane as a separator and carbon cloth as a current collector. The charge and discharge current density was 25.0 mA cm -2 .

[0276] The positive electrode of the battery is 5.0mL of 0.1M compound 1 dissolved in 1.0M NaCl solution, and the negative electrode is 11.0mL of 0.1M compound Vi-(SPr)2 dissolved in 1.0M NaCl solution. The test results of the compound in 1.0M NaCl are shown in Figure 2. Figure 51 As shown, the test results show that the performance of the compound is consistent with the cyclic voltammetry test, and the first cycle discharge capacity utilization rate is 96.0%.

[0277]

[0278] Example 26: Current Cycling Test (Compound 2)

[0279] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0280] The positive electrode of the battery is 7.0mL of 0.1M compound 2 dissolved in 1.0M NaCl solution, and the negative electrode is 11.0mL of 0.1M compound Vi-(SPr)2 dissolved in 1.0M NaCl solution. The test results of the compound in 1.0M NaCl show that the performance of the compound is consistent with the cyclic voltammetry test, and the coulombic efficiency is close to 100%.

[0281] Example 27: Current Cycling Test (Compound 3)

[0282] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0283] The positive electrode of the battery is 7.0mL of 0.1M compound 3 dissolved in 1.0M NaCl solution, and the negative electrode is 11.0mL of 0.1M compound Vi-(SPr)2 dissolved in 1.0M NaCl solution. The test results of the compound in 1.0M NaCl show that the performance of the compound is consistent with the cyclic voltammetry test, and the coulombic efficiency is close to 100%.

[0284] Example 28: Current Cycling Test (Compound 4)

[0285] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0286] The positive electrode of the battery is 7.0mL of 0.1M compound 4 dissolved in 1.0M NaCl solution, and the negative electrode is 11.0mL of 0.1M compound Vi-(SPr)2 dissolved in 1.0M NaCl solution. The test results of the compound in 1.0M NaCl are shown as follows. Figure 52 As shown, the test results show that the performance of the compound is consistent with the cyclic voltammetry test, with the first cycle discharge capacity utilization rate of 95.0% and the coulombic efficiency close to 100%.

[0287] Example 29: Current Cycling Test (Compound 5)

[0288] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0289] The positive electrode of the battery is 5.0mL of 0.1M compound 4 dissolved in 1.0M NaCl solution, and the negative electrode is 11.0mL of 0.1M compound Vi-(SPr)2 dissolved in 1.0M NaCl solution. The test results of the compound in 1.0M NaCl are shown in Figure 2. Figure 53 As shown, the test results show that the performance of the compound is consistent with the cyclic voltammetry test, with a discharge capacity utilization rate of 90% in the first cycle and a small amount of attenuation occurring in the cycle up to 900 cycles, with a decay rate of 0.1% / cycle.

[0290] Example 30: Current Cycling Test (Compound 6)

[0291] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm-2 .

[0292] The positive electrode of the battery is 7 mL of 0.1 M compound 6 dissolved in 1.0 M NaCl solution, and the negative electrode is 11.0 mL of 0. M compound Vi-(SPr)2 dissolved in 1.0 M NaCl solution. The test results of the compound in 1.0 M NaCl are as follows Figure 54 and Figure 55 As shown, the test results show that the performance of the compound is consistent with the cyclic voltammetry test, with a discharge capacity utilization rate of 94.0% in the first cycle, a small amount of attenuation occurring in the cycle up to 900 cycles, with a decay rate of 0.0033% / cycle (corresponding to 0.23% / day), and the coulombic efficiency is always greater than 99%.

[0293] Example 31: Current Cycling Test (Compound 7)

[0294] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0295] The positive electrode of the battery is 5.0mL of 0.1M compound 7 dissolved in 1.0M NaCl solution, and the negative electrode is 11.0mL of 0.1M compound Vi-(SPr)2 dissolved in 1.0M NaCl solution. The test results of the compound in 1.0M NaCl are shown in Figure 2. Figure 56 As shown, the test results show that the performance of the compound is consistent with the cyclic voltammetry test, with a discharge capacity utilization rate of 96% in the first cycle, a small amount of attenuation occurring in the cycle up to 100 cycles, and the coulombic efficiency always greater than 99%.

[0296] Example 32: Current Cycling Test (Compound 8)

[0297] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0298] The positive electrode of the battery is 5.0mL of 0.05M compound 8 dissolved in 1.0M NaCl solution, and the negative electrode is 11.0mL of 0.05M compound Vi-(SPr)2 dissolved in 1.0M NaCl solution. The test results of the compound in 1.0M NaCl are shown in Figure 2. Figure 57 As shown, the test results show that the performance of the compound is consistent with the cyclic voltammetry test, with a first-cycle discharge capacity utilization rate of 72.0%, and has redox activity as a positive electrode material.

[0299] Example 33: Current Cycling Test (Compound 9)

[0300] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0301] The positive electrode of the battery was 7.0mL of 0.1M compound 9 dissolved in 1.0M NaCl solution, and the negative electrode was 11.0mL of 0.1M compound Vi-(SPr)2 dissolved in 1.0M NaCl solution. The test results of the compound in 1.0M NaCl showed that the performance of the compound was consistent with the cyclic voltammetry test, and the coulombic efficiency was close to 100%.

[0302] Example 34: Current Cycling Test (Compound 10)

[0303] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0304] The positive electrode of the battery is 7 mL of 0.1 M compound 10 dissolved in 1.0 M KCl solution, and the negative electrode is 5.0 mL of 0.1 M compound 1,8-ESP dissolved in 1.0 M KCl solution. The test results of the compound in 1.0 M KCl are shown as follows: Figure 58 and Figure 59 As shown, the test results show that the performance of the compound is consistent with the cyclic voltammetry test, with a discharge capacity utilization rate of 99.0% in the first cycle, and a capacity utilization rate of up to 99.0% without any attenuation in the cycle of up to 900 cycles, and the coulombic efficiency is always greater than 99.0%.

[0305] Example 35: Current Cycling Test (Compound 11)

[0306] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0307] The battery's positive electrode consisted of 7.0 mL of 0.1 M compound 11 dissolved in 1.0 M NaCl, and the negative electrode consisted of 11.0 mL of 0.1 M compound Vi-(SPr)2 dissolved in 1.0 M NaCl. Testing of the compound in 1.0 M NaCl showed consistent performance with cyclic voltammetry, with a coulombic efficiency approaching 100%.

[0308] Example 36: Current Cycling Test (Compound 12)

[0309] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0310] The battery's positive electrode consisted of 7.0 mL of 0.1 M compound 12 dissolved in 1.0 M NaCl, and the negative electrode consisted of 11.0 mL of 0.1 M compound Vi-(SPr)2 dissolved in 1.0 M NaCl. Testing of the compound in 1.0 M NaCl showed consistent performance with cyclic voltammetry, with a coulombic efficiency greater than 99%.

[0311] Example 37: Current Cycling Test (Compound 13)

[0312] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0313] The battery's positive electrode consisted of 7.0 mL of 0.1 M compound 13 dissolved in 1.0 M NaCl, and the negative electrode consisted of 11.0 mL of 0.1 M compound Vi-(SPr)2 dissolved in 1.0 M NaCl. Testing of the compound in 1.0 M NaCl showed consistent performance with cyclic voltammetry, with a coulombic efficiency approaching 100%.

[0314]

[0315] Example 38: Current Cycling Test (Compound 14)

[0316] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0317] The positive electrode of the battery is 7 mL of 0.1 M compound 14 dissolved in 1.0 M KCl solution, and the negative electrode is 20.0 mL of 0.1 M compound Vi-(SPr)2 dissolved in 1.0 M KCl solution. The test results of the compound in 1.0 M KCl are shown as follows: Figure 60 and Figure 61 As shown, the test results show that the performance of the compound is consistent with the cyclic voltammetry test, with a first-cycle discharge capacity utilization rate of 93.7%, showing redox activity as a positive electrode material. The coulombic efficiency is 99.9%.

[0318] Example 39: Current Cycling Test (Compound 15)

[0319] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0320] The positive electrode of the battery is 5.0 mL of 0.1 M compound 15 dissolved in 1.0 M KCl solution, and the negative electrode is 10.0 mL of 0.1 M compound Vi-(SPr)2 dissolved in 1.0 M KCl solution. The test results of the compound in 1.0 M KCl are shown in Figure 2. Figure 62 and 63 As shown, the test results show that the performance of the compound is consistent with the cyclic voltammetry test, with a gradual increase in discharge capacity to a final utilization rate of 76.6%, achieving 1125 cycles, and having redox activity as a positive electrode material. The coulombic efficiency is 99.9%.

[0321] Example 40: Current Cycling Test (Compound 16)

[0322] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0323] The positive electrode of the battery is 5.0mL of 0.1M compound 16 dissolved in 1.0M KCl solution, and the negative electrode is 10mL of 0.1M compound Vi-(SPr)2 dissolved in 1.0M KCl solution. The test results of the compound in 1.0M KCl are shown in Figure 2. Figure 64 and Figure 65 As shown, the test results show that the performance of the compound is consistent with the cyclic voltammetry test, with a first-cycle discharge capacity utilization of 80.0%, and has redox activity as a positive electrode material. The coulombic efficiency is 99.0%.

[0324] Example 41: Current Cycling Test (Compound 17)

[0325] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0326] The positive electrode of the battery is 5.0mL of 0.1M compound 17 dissolved in 1.0M KCl solution, and the negative electrode is 10mL of 0.1M compound Vi-(SPr)2 dissolved in 1.0M KCl solution. The test results of the compound in 1.0M KCl are shown as follows. Figure 66 and Figure 67 As shown, the test results show that the performance of the compound is consistent with the cyclic voltammetry test, with a gradual increase in discharge capacity to a final utilization rate of 82.7%, achieving 1312 cycles, and having redox activity as a positive electrode material. The coulombic efficiency is 99.9%.

[0327] Example 42: Current Cycling Test (Compound 18)

[0328] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0329] The positive electrode of the battery is 5.0 mL of 0.1 M compound 18 dissolved in 1.0 M KCl solution, and the negative electrode is 10 mL of 0.1 M compound Vi-(SPr)2 dissolved in 1.0 M KCl solution. The test results of the compound in 1.0 M KCl are shown in Figure 2. Figure 68 and Figure 69 As shown, the test results show that the compound's performance is consistent with the cyclic voltammetry test, with a first-cycle discharge capacity utilization rate of 74.4% and a cycle life of 689 cycles, demonstrating its redox activity as a positive electrode material. A gradual attenuation rate of 0.033% / cycle (corresponding to 4% / day) was observed during the cycle, and the coulombic efficiency was 99.9%.

[0330] Example 43: Current Cycling Test (Compound 10)

[0331] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using ion-selective membranes as separators and carbon cloth or carbon felt as current collector materials. The charge-discharge current density was 25.0 mA cm -2 .

[0332] The positive electrode of the battery is 7.0mL of 0.1M compound 10 dissolved in 1.0M KCl solution, the negative electrode is zinc foil lined with carbon felt on the negative side, and the mobile solution is 30mL of 0.1M ZnCl2 dissolved in 1.0M KCl solution. The test results of the compound in 1.0M KCl are shown below. Figure 70 and Figure 71 As shown, the test results show that the compound's performance is consistent with the cyclic voltammetry test, with a first-cycle discharge capacity utilization rate of 88.3% and a cycle life of 457 cycles, demonstrating its redox activity as a positive electrode material. A gradual attenuation rate of 0.021% / cycle was observed during the cycle, and the coulombic efficiency was greater than 98%.

[0333] Example 44: Current Cycling Test (Compound 19)

[0334] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0335] The positive electrode of the battery is 7 mL of 0.1 M compound 19 dissolved in 1.0 M KCl solution, and the negative electrode is 10.0 mL of 0.1 M compound Vi-(SPr)2 dissolved in 1.0 M KCl solution. The test results of the compound in 1.0 M KCl are shown as follows: Figure 72 and Figure 73 As shown, the test results show that the performance of the compound is consistent with the cyclic voltammetry test. The discharge capacity utilization rate in the first cycle is less than 99.0%. The capacity slowly decreases in the first 20 cycles, and the capacity utilization rate can reach 99.0%. The coulombic efficiency is always greater than 99.0%.

[0336] Example 45: Current Cycling Test (Compound 20)

[0337] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 50.0 mA cm -2 .

[0338] The positive electrode of the battery is 5 mL of 0.1 M compound 20 dissolved in 1.0 M KCl solution, and the negative electrode is 10.0 mL of 0.1 M compound Vi-(SPr)2 dissolved in 1.0 M KCl solution. The test results of the compound in 1.0 M KCl are shown as follows: Figure 74 and Figure 75 As shown, the test results show that the performance of the compound is consistent with the cyclic voltammetry test, and it has redox activity as a positive electrode material, and the coulombic efficiency is always greater than 99.0%.

[0339] Example 46: Current Cycling Test (Compound 21)

[0340] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0341] The positive electrode of the battery was 7.0mL of 0.1M compound 21 dissolved in 1.0M NaCl solution, and the negative electrode was 11.0mL of 0.1M compound Vi-(SPr)2 dissolved in 1.0M NaCl solution. The test results of the compound in 1.0M NaCl showed that the performance of the compound was consistent with the cyclic voltammetry test, and the coulombic efficiency was close to 100%.

[0342] Example 47: Current Cycling Test (Compound 22)

[0343] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0344] The positive electrode of the battery is 7 mL of 0.1 M compound 22 dissolved in 1.0 M KCl solution, and the negative electrode is 5.0 mL of 0.1 M compound 1,8-ESP dissolved in 1.0 M KCl solution. The test results of the compound in 1.0 M KCl are shown as follows: Figure 76 and Figure 77 As shown, the test results show that the performance of the compound is consistent with the cyclic voltammetry test, achieving 640 cycles, having redox activity as a positive electrode material, and the coulombic efficiency is always greater than 99.0%.

[0345] Example 48: Current Cycling Test (Compound 23)

[0346] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0347] The positive electrode of the battery was 7.0mL of 0.1M compound 23 dissolved in 1.0M NaCl solution, and the negative electrode was 11.0mL of 0.1M compound Vi-(SPr)2 dissolved in 1.0M NaCl solution. The test results of the compound in 1.0M NaCl showed that the performance of the compound was consistent with the cyclic voltammetry test, and the coulombic efficiency was close to 100%.

[0348] Example 49: Current Cycling Test (Compound 24)

[0349] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0350] The positive electrode of the battery was 7.0 mL of 0.1 M compound 24 dissolved in 1.0 M NaCl solution, and the negative electrode was 11.0 mL of 0.1 M compound Vi-(SPr)2 dissolved in 1.0 M NaCl solution. The test results of the compound in 1.0 M NaCl showed that the performance of the compound was consistent with the cyclic voltammetry test, with a coulombic efficiency greater than 99%.

[0351] Example 50: Current Cycling Test (Compound 25)

[0352] The current cycling test was performed using an electrochemical workstation to perform constant current charge-discharge cycle tests. The synthesized compounds were used to assemble batteries, using an ion-selective permeable membrane as a separator and carbon cloth as a current collector. The charge-discharge current density was 25.0 mA cm -2 .

[0353] The positive electrode of the battery was 7.0mL of 0.1M compound 25 dissolved in 1.0M NaCl solution, and the negative electrode was 11.0mL of 0.1M compound Vi-(SPr)2 dissolved in 1.0M NaCl solution. The test results of the compound in 1.0M NaCl showed that the performance of the compound was consistent with the cyclic voltammetry test, and the coulombic efficiency was close to 100%.

[0354] The above-mentioned specific implementation methods are used to illustrate the present invention and are only preferred embodiments of the present invention, rather than limiting the present invention. Any modifications, equivalent substitutions, improvements, etc. made to the present invention within the spirit of the present invention and the scope of protection of the claims shall fall within the scope of protection of the present invention.

Claims

1. A novel iron-based complex, characterized in that: The structural formula of the novel iron-based complex is shown below: in, is a substituted or unsubstituted 5-12 membered nitrogen-containing heteroaromatic ring, a substituted or unsubstituted 5-12 membered oxygen-containing heteroaromatic ring, a substituted or unsubstituted 5-12 membered sulfur-containing heteroaromatic ring, or a carbon carbene structure; M 1 Selected from the group consisting of Fe(II), Fe(III); R 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from the following group: H, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted 5-12 membered heterocycloalkyl or aryl, substituted or unsubstituted C6-C10 aryl, mercapto (-S - or -SH), nitro (-NO2), cyano (-CN), halogen (-F or -Cl or -Br), -COOY, -SO3Y, -PO3Y, -NH2·HQ, -NHZ·HQ, -N(Z)2·HQ, -N + (Z) 3X; wherein Y is selected from the group consisting of: H + NH4 + 、Li + 、Na + , K + Mg 2 + 、Al 3+ , Ca 2+ ;Q - Select from the following group: F - 、Cl-、Br - , I - OH - 、OAc - ,OTf - ,OTs - 、SO4 2- 、SO3 2- PO4 3- 、HPO4 2- 、H2PO4 - 、NO2 - 、NO3 - 、CO3 2- 、HCO3 - 、ClO4 - 、ClO3 - 、ClO2 - , ClO - 、CN - ; Z is selected from the following group: substituted or unsubstituted C1-C10 alkyl; X is selected from the following group: F - 、Cl - Br - , I - 、OH-、OAc - 、OTf-、OTs - 、SO4 2- 、SO3 2- PO4 3- <h2 style=";text-align:left;direction:ltr">HPO4<h2 style=";text-align:left;direction:ltr"> 2- <h2 style=";text-align:left;direction:ltr"> H2PO4<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> NO2<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> NO3<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> CO3<h2 style=";text-align:left;direction:ltr"> 2- <h2 style=";text-align:left;direction:ltr"> HCO3<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ClO4<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ClO3<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ClO2<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ClO<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> CN<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ; Among them, R 6 The position of the substituent is One or more hydrogen atoms in the parent core structure are replaced, or the substituent is located on a heteroatom, R 6 Selected from the group consisting of H, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted 5-12 membered heterocycloalkyl or aryl, substituted or unsubstituted C6-C10 aryl, thiol (-S - or -SH), nitro (-NO2), cyano (-CN), halogen (-F or -Cl or -Br), -COOY, -SO3Y, -PO3Y, -NH2·HQ, -NHZ·HQ, -N(Z)2·HQ, -N + (Z) 3X; wherein Y is selected from the group consisting of: H + NH4 + 、Li + 、Na + , K + Mg 2+ 、Al 3+ , Ca 2+ ;Q - Select from the following group: F - 、Cl - Br - , I - OH - 、OAc - ,OTf - ,OTs - 、SO4 2- 、SO3 2- PO4 3- 、HPO4 2- 、H2PO4 - 、NO2 - 、NO3 - 、CO3 2- 、HCO3 - 、ClO4 - 、ClO3 - 、ClO2 - , ClO - 、CN - ; Z is selected from the following group: substituted or unsubstituted C1-C10 alkyl; X is selected from the following group: F - 、Cl - Br - , I - OH - 、OAc - ,OTf - ,OTs - 、SO4 2- 、SO3 2- PO4<h2 style=";text-align:left;direction:ltr"> 3- <h2 style=";text-align:left;direction:ltr"> HPO4<h2 style=";text-align:left;direction:ltr"> 2- <h2 style=";text-align:left;direction:ltr"> H2PO4<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> NO2<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> NO3<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> CO3<h2 style=";text-align:left;direction:ltr"> 2- <h2 style=";text-align:left;direction:ltr"> HCO3<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ClO4<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ClO3<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ClO2<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ClO<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> CN<h2 style=";text-align:left;direction:ltr"> - <h2 style=";text-align:left;direction:ltr"> ; x, y are selected from the following group: 0-20; The new iron-based complex is electrically neutral; M 2 is at least one charge-balancing ion, wherein the charge-balancing ion is a cation or anion; the cation is selected from the group consisting of: + NH4 + 、Li + 、Na + , K + Mg 2+ 、Al 3+ , Ca 2+ ; The anion is selected from the following group: F - 、Cl - Br - , I - OH - 、OAc - ,OTf - ,OTs - 、SO4 2- 、SO3 2- PO4 3- 、HPO4 2- 、H2PO4 - 、NO2 - 、NO3 - 、CO3 2- 、HCO3 - 、ClO4 - 、ClO3 - 、ClO2 - , ClO - 、CN - .

2. The novel iron-based complex according to claim 1, characterized in that: The substituted or unsubstituted 5-12 nitrogen-containing heteroaromatic ring is selected from the following groups:

3. The novel iron-based complex according to claim 1, characterized in that: The substituted or unsubstituted 5-12 membered oxygen-containing heteroaromatic ring is selected from the following groups:

4. The novel iron-based complex according to claim 1, characterized in that: The substituted or unsubstituted 5-12 membered sulfur-containing heteroaromatic ring is selected from the following groups:

5. The novel iron-based complex according to claim 1, characterized in that: The carbon carbene structure is selected from the group consisting of:

6. The novel iron-based complex according to claim 1, characterized in that: is a substituted or unsubstituted 5-12-membered nitrogen-containing heteroaromatic ring, and the structural formula of the novel iron-based complex is shown below: The coordination form of the above nitrogen-containing heteroaromatic ring is as follows:

7. The novel iron-based complex according to claim 1, characterized in that: is a substituted or unsubstituted 5-12-membered oxygen-containing heteroaromatic ring, and the structural formula of the novel iron-based complex is shown below: The coordination form of the above oxygen-containing heteroaromatic ring is as follows:

8. The novel iron-based complex according to claim 1, characterized in that: is a substituted or unsubstituted 5-12 membered sulfur-containing heteroaromatic ring, and the structural formula of the novel iron-based complex is shown below: The coordination form of the above sulfur-containing heteroaromatic ring is as follows:

9. The novel iron-based complex according to claim 1, characterized in that: It is a substituted or unsubstituted carbon carbene compound, and the structural formula of the novel iron-based complex is shown below: The coordination forms of the above nitrogen-containing heterocarbon carbenes are shown below:

10. Use of the novel iron-based complex according to any one of claims 1 to 9 in electrochemical energy storage.

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