Naphthalene-type compounds, their production methods and uses

Abstract

The present invention discloses naphthalene-type compounds and their preparation and use. The naphthalene-type compounds have a molecular structure substituted with multiple hydroxyl groups, multiple benzylamine groups, and quaternary ammonium groups or multiple quaternary ammonium functional groups, and have significantly improved water solubility in acidic aqueous solutions compared to the raw materials. The electrochemical reaction requires low raw material costs, high reaction yields, and proceeds under ambient temperature and pressure conditions without the need for additional catalysts. It can be carried out under air conditions without the need for inert gas protection.

Description

[Technical Field]

[0001] The present invention belongs to the field of electrochemical synthesis, and specifically relates to naphthalene-type compounds and their preparation methods and uses. [Background technology]

[0002] Aromatic compounds possess stable skeletal structures and large conjugate structures, making them suitable for aqueous energy storage applications. However, because many fused-ring aromatic hydrocarbons have hydrophobic structures, their water solubility must be improved by hydrophilic modification. Naphthalene derivatives possess rigid structures and moderate molecular weights, making them promising active materials for aqueous energy storage. Based on the correlation between molecular structure and activity, methods for improving solubility by introducing hydrophilic functional groups into aromatic compounds have been studied. Common hydrophilic functional groups include sulfonic acid groups, amine groups (primary, secondary, tertiary, and quaternary), carboxyl groups, and phosphate groups. Synthetic strategies for easily and efficiently incorporating these hydrophilic groups into naphthalene derivatives have been extensively studied. Wang et al. synthesized naphthoquinone derivatives bearing carboxyl groups by cyclization using oxalyl chloride via the Friedel-Crafts reaction followed by hydrolysis under alkaline conditions. This compound showed a solubility of 1.2 mol / L in 2M KOH solution (ACS Energy Lett. 2018, 3, 2404-2409). Tong et al. prepared a binaphthol compound (bilawsone) using a radical-initiated dimerization method and achieved a solubility of 0.56 mol / L in an aqueous environment at pH = 14 (ACS Energy Lett. 2019, 4, 1880-1887). Furthermore, a sulfonate-modified naphthoquinone derivative showed a solubility of 0.9 mol / L in 1 mol / L KOH (Sci. Rep. 2016, 6, 39101). Summary of the Invention [Problem to be solved by the invention]

[0003] Few studies have been reported on the solubility enhancement of naphthalene derivatives in acidic environments, and there is room for further improvement in the solubility of naphthalene-type compounds. [Means for solving the problem]

[0004] According to one aspect of the present application, there is provided a naphthalene-type compound, which is a water-soluble polysubstituted naphthalene-type compound: the naphthalene-type compound includes a naphthoquinone-type compound and / or a naphthol-type compound, The naphthoquinone compound has any one of the structures represented by formula (1), formula (2), and formula (3), The naphthol compound is a naphthalene-type compound having any one of the structures represented by formula (4), formula (5), and formula (6). JPEG2026502426000002.jpg34170JPEG2026502426000003.jpg34170JPEG2026502426000004.jpg52170JPEG2026502426000005.jpg35170JPEG2026502426000006.jpg35170JPEG2026502426000007.jpg52170Naphthalene-type compounds having structures represented by formula (1), formula (2), and formula (3) are oxidized naphthalene-type compounds, The naphthalene-type compounds having the structures represented by formula (4), formula (5), and formula (6) are reduced naphthalene-type compounds, An oxidized naphthalene compound having a structure represented by formula (1) and a reduced naphthalene compound having a structure represented by formula (4) form a pair of redox couples, An oxidized naphthalene compound having a structure represented by formula (2) and a reduced naphthalene compound having a structure represented by formula (5) form a pair of redox couples, An oxidized naphthalene compound having a structure represented by formula (3) and a reduced naphthalene compound having a structure represented by formula (6) form a pair of redox couples, R 11 , R 12 , R 21, R 22 , R 31 , R 32 are independently selected from H, F, Cl, Br, I, hydroxyl, methoxyl, carboxyl, a sulfonic acid group, a cyano group, —NR2, a C1-C6 aliphatic group, or a C1-C6 aliphatic group having a substituent X—; A naphthalene-type compound, wherein the substituent X- in the C1-C6 aliphatic group having the substituent X- is selected from carboxyl, a sulfonic acid group, a phosphonic acid group, hydroxyl, methoxyl, or trimethylamino.

[0005] In a second aspect, the present application provides a method for preparing the above naphthalene-type compound, comprising the steps of: The substrate and the acid are mixed, and electrochemical charging is carried out to obtain naphthoquinone compounds, followed by electrochemical discharging to obtain naphthol compounds.

[0006] Alternatively, the substrate has the structure of formula (7): JPEG2026502426000008.jpg36170R 11 , R 21 , R 31 , R 41 , R 12 , R 22 , R 32 , R 42 are independently any one of H, F, Cl, Br, I, a hydroxyl group, a methoxy group, a carboxyl group, a sulfonic acid group, -NR2, a C1-C6 aliphatic group, or a C1-C6 aliphatic group having a substituent X-, and R 11 , R 21 , R 31 , R 41 , R 12 , R 22 , R 32 , R 42 at least one of which is a hydroxyl group, The substituent X- is any one of a carboxyl group, a sulfonic acid group, a phosphonic acid group, a hydroxyl group, a methoxy group, and a trimethylamino group.

[0007] Optionally, the acid comprises at least one of sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, citric acid, trifluoroacetic acid, and trifluoromethanesulfonic acid; The concentration of the acid is 0.1 to 5 mol / L, and preferably the acid concentration range is 2 to 3 mol / L.

[0008] Alternatively, the concentration of the acid can be 0.1 mol / L, 0.5 mol / L, 1 mol / L, 2 mol / L, 3 mol / L, 4 mol / L, 5 mol / L, or a range between any two of these values.

[0009] Optionally, the electrochemical charging and discharging steps are carried out in an electrochemical reaction cell or an aqueous battery.

[0010] Optionally, when the electrochemical charging and discharging processes are carried out in an electrochemical reaction cell, a three-electrode system is used, in which graphite plates are the working electrode and the counter electrode, and the reference electrode is one of a silver-silver chloride electrode, a saturated calomel electrode, or a mercury-mercurous sulfate electrode.

[0011] Alternatively, when the electrochemical process is performed in an electrochemical reaction cell, the scan rate is 5 to 500 mVs. -1 and the voltage range is 0 to 1 V. The electrochemical reaction starts from the raw material, and first undergoes electrochemical oxidation to obtain naphthoquinone compounds, and then undergoes electrochemical reduction to obtain naphthol compounds. The order cannot be reversed. Therefore, the reaction process requires a low voltage (0 V) to a high voltage (1 V) Electrochemical charge-oxidation to , followed by electrochemical discharge-reduction from a high voltage (1 V) to a low voltage (0 V), The charging voltage range is 0.23 to 0.35 V (vs. SCE). The discharge voltage range is 0.15 to 0.25 V (vs. SCE).

[0012] Optionally, when the electrochemical charging and discharging steps are performed in an aqueous battery, the charging and discharging are performed in a constant current mode; The side containing the substrate and the acid is the positive electrode, and the negative electrode contains the conjugated redox compound; The conjugated redox compound is TiO 2+ / Ti 3+ , V 3+ / V 2+ or heteropolyacid (silicotungstic acid), When the electrochemical reaction process is carried out in an aqueous battery, it is necessary to first perform electrochemical oxidation (charging) to obtain a naphthoquinone compound, and then perform electrochemical reduction (discharging) to obtain a naphthol compound, and the initial state of the conjugated redox compound on the negative electrode side must be in an oxidized state. When the electrochemical reaction process is carried out in an aqueous battery, the theoretical capacity of the negative electrode electrolyte must be at least twice the product capacity obtained in the positive electrode electrochemical reaction. Current density is 1 to 120 mAcm -2 and The charge cut-off voltage is 1.2 to 1.4 V. The discharge end voltage is 0 to 0.1V.

[0013] Alternatively, the water-soluble polysubstituted naphthalene-type compound may be prepared as follows: JPEG2026502426000009.jpg83170

[0014] The solubility of the substrate in an acidic aqueous solution varies greatly depending on the type of substituent, and the state of the prepared substrate solution may be a clear solution or a muddy suspension containing undissolved solutes.

[0015] The corresponding naphthoquinone or naphthol compounds obtained by the electrochemical reaction have structures that are clearly different from those of the substrate, and therefore their solubility is significantly improved. As the reaction progresses, the partially turbid suspension is observed to change into a transparent solution.

[0016] In a third aspect, the present application provides an aqueous redox battery, the aqueous redox battery comprising an electrolyte; the electrolyte solution includes a positive electrode electrolyte solution and a negative electrode electrolyte solution, the positive electrode electrolyte contains a naphthoquinone-type compound in the naphthalene-type compound or a naphthoquinone-type compound in the naphthalene-type compound produced by the production method, and / or The negative electrode electrolyte contains a naphthol compound in the naphthalene-type compound or a naphthol compound in the naphthalene-type compound produced by the production method.

[0017] In a fourth aspect, the present application provides a flow battery, the flow battery being a naphthalene-type flow battery that operates stably in air and has a long life; the flow cell includes an electrolyte; the electrolyte solution includes a positive electrode electrolyte solution and a negative electrode electrolyte solution, the electrolyte solution contains a naphthalene-type compound; the naphthalene-type compound includes a naphthoquinone-type compound (oxidized form) and / or a naphthol-type compound (reduced form), the positive electrode electrolyte contains a naphthoquinone-type compound in the naphthalene-type compound, and the negative electrode electrolyte contains a naphthol-type compound in the naphthalene-type compound, Or, the positive electrode electrolyte contains a naphthol-type compound in the naphthalene-type compound, and the negative electrode electrolyte contains a naphthoquinone-type compound in the naphthalene-type compound, the concentration of the naphthalene-type compound in the positive electrode electrolyte or the negative electrode electrolyte is 0.01 to 3 mol / L; the naphthoquinone compound is a naphthoquinone compound in the naphthalene-type compound, or a naphthoquinone compound in the naphthalene-type compound produced by the production method, The naphthol compound is a naphthol compound in the naphthalene type compound or a naphthol compound in the naphthalene type compound produced by the production method.

[0018] Optionally, the concentration of the naphthalene-type compound in the positive electrode electrolyte or the negative electrode electrolyte is 0.01 to 1.8 mol / L.

[0019] Optionally, the concentration of the naphthalene-type compound in the positive electrode electrolyte or the negative electrode electrolyte is 0.01 to 1.5 mol / L.

[0020] Optionally, the concentration of the naphthalene-type compound in the positive electrode electrolyte or the negative electrode electrolyte is 1.0 to 1.5 mol / L.

[0021] Alternatively, the concentration of the naphthalene-type compound in the cathode electrolyte or anode electrolyte can be any of 0.01 mol / L, 0.05 mol / L, 0.1 mol / L, 0.5 mol / L, 1 mol / L, 1.5 mol / L, or a range between any two of these values.

[0022] The naphthoquinone compound has any one of the structures represented by formula (1), formula (2), and formula (3), The naphthol compound is a naphthalene-type compound having any one of the structures represented by formula (4), formula (5), and formula (6). JPEG2026502426000010.jpg34170JPEG2026502426000011.jpg34170JPEG2026502426000012.jpg52170JPEG2026502426000013.jpg35170JPEG2026502426000014.jpg35170JPEG2026502426000015.jpg52170Naphthalene-type compounds having structures represented by formula (1), formula (2), and formula (3) are oxidized naphthalene-type compounds, The naphthalene-type compounds having the structures represented by formula (4), formula (5), and formula (6) are reduced naphthalene-type compounds, An oxidized naphthalene compound having a structure represented by formula (1) and a reduced naphthalene compound having a structure represented by formula (4) form a pair of redox couples, An oxidized naphthalene compound having a structure represented by formula (2) and a reduced naphthalene compound having a structure represented by formula (5) form a pair of redox couples, An oxidized naphthalene compound having a structure represented by formula (3) and a reduced naphthalene compound having a structure represented by formula (6) form a pair of redox couples, R 11 , R 12 , R 21 , R 22 , R 31 , R 32 are independently selected from H, F, Cl, Br, I, hydroxyl, methoxyl, carboxyl, a sulfonic acid group, a cyano group, —NR2, a C1-C6 aliphatic group, or a C1-C6 aliphatic group having a substituent X—; The substituent X- in the C1-C6 aliphatic group having the substituent X- is selected from carboxyl, a sulfonic acid group, a phosphonic acid group, hydroxyl, methoxyl, or trimethylamino.

[0023] Optionally, the electrochemical reaction equation in the liquid flow battery is as follows: JPEG2026502426000016.jpg107170

[0024] Optionally, the positive electrode electrolyte or the negative electrode electrolyte further comprises a conjugated redox compound; The conjugated redox compound is TiO 2+ / Ti 3+ , V 3+ / V 2+ , and at least one heteropolyacid, The heteropolyacid includes silicotungstic acid.

[0025] Optionally, the electrolyte further comprises an acid; the acid includes at least one of sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, citric acid, trifluoroacetic acid, and trifluoromethanesulfonic acid; The concentration of the acid is 0.01 to 6 mol / L.

[0026] Optionally, the concentration of the acid can be any of 0.01 mol / L, 0.05 mol / L, 0.1 mol / L, 0.5 mol / L, 1 mol / L, 2 mol / L, 3 mol / L, 4 mol / L, 5 mol / L, 6 mol / L, or a range between any two of these values.

[0027] Alternatively, the type and concentration of the acid contained in the positive electrode electrolyte and the negative electrode electrolyte may be the same, thereby effectively reducing the problem of imbalance in volume and concentration of the positive and negative electrode electrolytes due to solvent migration.

[0028] Alternatively, the naphthalene-type compound can be obtained by the following process: The substrate and the acid are mixed, and electrochemical charging is carried out to obtain naphthoquinone compounds, followed by electrochemical discharging to obtain naphthol compounds.

[0029] Alternatively, the substrate has the structure of formula (7): JPEG2026502426000017.jpg36170R 11 , R 21 , R 31 , R 41 , R 12 , R 22 , R 32 , R 42 are independently any one of H, F, Cl, Br, I, a hydroxyl group, a methoxy group, a carboxyl group, a sulfonic acid group, -NR2, a C1-C6 aliphatic group, or a C1-C6 aliphatic group having a substituent X-, and R 11 , R 21 , R 31 , R 41 , R 12 , R 22 , R 32 , R 42 at least one of which is a hydroxyl group, The substituent X- is any one of a carboxyl group, a sulfonic acid group, a phosphonic acid group, a hydroxyl group, a methoxy group, and a trimethylamino group.

[0030] Optionally, the acid comprises at least one of sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, citric acid, trifluoroacetic acid, and trifluoromethanesulfonic acid; The concentration of the acid is 0.1 to 5 mol / L, and preferably the acid concentration range is 2 to 3 mol / L.

[0031] Alternatively, the concentration of the acid can be 0.1 mol / L, 0.5 mol / L, 1 mol / L, 2 mol / L, 3 mol / L, 4 mol / L, 5 mol / L, or a range between any two of these values.

[0032] The electrochemical charging and discharging steps are carried out in an electrochemical reaction cell or an aqueous battery.

[0033] When the electrochemical charging and discharging processes are carried out in an electrochemical reaction cell, a three-electrode system is used, with graphite plates as the working electrode and counter electrode, and the reference electrode is one of a silver-silver chloride electrode, a saturated calomel electrode, or a mercury-mercurous sulfate electrode.

[0034] When the electrochemical process is performed in an electrochemical reaction cell, the scan rate is 5 to 500 mVs. -1 and the voltage range is 0 to 1 V. The electrochemical reaction starts from the raw material, and first undergoes electrochemical oxidation to obtain naphthoquinone compounds, and then undergoes electrochemical reduction to obtain naphthol compounds. The order cannot be reversed. Therefore, the reaction process requires a low voltage (0 V) to a high voltage (1 V) This is followed by electrochemical charge-oxidation from a high voltage (1 V) to a low voltage (0 V).

[0035] The charging voltage range is 0.23 to 0.35 V (vs. SCE). The discharge voltage range is 0.15 to 0.25 V (vs. SCE).

[0036] When the electrochemical charging and discharging steps are performed in an aqueous battery, the charging and discharging are performed in a constant current mode; The side containing the substrate and the acid is the positive electrode, and the negative electrode contains the conjugated redox compound; The conjugated redox compound is TiO 2+ / Ti 3+ , V 3+ / V 2+ or heteropolyacid (silicotungstic acid).

[0037] When the electrochemical reaction process is carried out in an aqueous battery, it is necessary to first perform electrochemical oxidation (charging) to obtain a naphthoquinone compound, and then perform electrochemical reduction (discharging) to obtain a naphthol compound, and the initial state of the conjugated redox compound on the negative electrode side must be in an oxidized state.

[0038] When the electrochemical reaction process is carried out in an aqueous battery, the theoretical capacity of the negative electrode electrolyte must be at least twice the product capacity obtained in the positive electrode electrochemical reaction.

[0039] Current density is 1 to 120 mAcm -2 and The charge cut-off voltage is 1.2 to 1.4 V. The discharge end voltage is 0 to 0.1V.

[0040] The process for preparing the water-soluble polysubstituted naphthalene-type compound is as follows. JPEG2026502426000018.jpg83170

[0041] The solubility of the substrate in an acidic aqueous solution varies greatly depending on the type of substituent, and the state of the prepared substrate solution may be a clear solution or a muddy suspension containing undissolved solutes.

[0042] The corresponding naphthoquinone or naphthol compounds obtained by the electrochemical reaction have structures that are clearly different from those of the substrate, and therefore their solubility is significantly improved. As the reaction progresses, the partially turbid suspension is observed to change into a transparent solution. [Effects of the Invention]

[0043] Compared with the prior art, the water-soluble poly-substituted naphthalene-type compounds prepared by electrochemical methods provided by the present invention have the following advantages: 1) The electrochemical reaction requires low raw material costs, has a high reaction yield, and proceeds under normal temperature and pressure conditions without the need for an additional catalyst. While other organic redox couples are easily oxidized, causing couple inactivation and irreversible side reactions or capacity degradation, the compound of the present invention is an organic redox couple that can stably operate under air conditions, exhibiting air insensitivity and a long cycle life. 2) The water solubility of the naphthalene-type compounds is significantly improved. 3) The naphthalene-type compounds have a polysubstituted structure, and it is difficult to obtain such a polysubstituted structure through a simple synthetic route under ordinary reaction conditions. 4) In the flow cell, the naphthalene-type compound has low raw material costs, a simple manufacturing process, and a high product yield. 5) In the flow battery, the synthesis process of the naphthalene-type compound is scalable and compatible with the large-scale energy storage characteristics of the flow battery. 6) In the flow-through battery, the naphthalene-type compound exhibits excellent stability and shows no significant capacity degradation even during charge-discharge cycles in an air environment, in contrast to other organic redox couples, which are easily oxidized, causing couple inactivation and irreversible side reactions and capacity degradation. 7) In the liquid flow battery, the large conjugated structure and polysubstituted molecular structure of the naphthalene-type compound function as a couple with excellent molecular stability, reducing the probability of side reactions occurring and reducing the risk of cross-contamination due to membrane permeation. [Brief explanation of the drawings]

[0044] [Figure 1]This is a cyclic voltammogram obtained when 3-benzylamine-2-hydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone-type compound) and 1,2,3-trihydroxy-3-benzylaminenaphthalene (a naphthol-type compound) were produced in an electrochemical reaction cell using 2,4-dibenzylamine-1-naphthol as a substrate in Example 1. Measurement conditions: graphite was used as the working electrode and counter electrode, and a saturated calomel electrode was used as the reference electrode, with a sweep rate of 50 mV / s. [Figure 2] This is a photograph of the actual cathode electrolyte used in producing 3-benzylamine-2-hydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) in an aqueous redox cell using 2,4-dibenzylamine-1-naphthol as the substrate in Example 2. The suspension on the left is a 3 mol / L sulfuric acid solution of 0.1 mol / L 2,4-dibenzylamine-1-naphthol, and the clear liquid on the right is a 3 mol / L sulfuric acid solution of 3-benzylamine-2-hydroxy-1,4-dicarbonylnaphthalene, the electrochemical oxidation product. [Figure 3] Cyclic voltammograms obtained when 3,5,7-tribenzylamine-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone-type compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminenaphthalene (a naphthol-type compound) were produced in an electrochemical reaction cell using 2,4,6,8-tetrabenzylamine-1,5-naphthodiol as a substrate in Example 3. Measurement conditions: graphite was used as the working electrode and counter electrode, and a saturated calomel electrode was used as the reference electrode, with a sweep rate of 50 mV / s. [Figure 4] In Example 4, the characteristic molecular weight was obtained by mass spectrometry of the raw material in the process of producing 3,5,7-tribenzylamine-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) using 2,4,6,8-tetrabenzylamine-1,5-naphthodiol as a substrate in an aqueous redox cell. [Figure 5]In Example 4, in the process of producing 3,5,7-tribenzylamine-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) using 2,4,6,8-tetrabenzylamine-1,5-naphthodiol as a substrate in an aqueous redox cell, the electrochemical oxidation product 3,5,7-tribenzylamine-2,8-dihydroxy-1,4-dicarbonylnaphthalene was analyzed by mass spectrometry to obtain a characteristic molecular weight. [Figure 6] In Example 4, the characteristic molecular weight was obtained by mass spectrometry of 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminenaphthalene (a naphthol compound) during the production of 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminenaphthalene using 2,4,6,8-tetrabenzylamine-1,5-naphthodiol as a substrate in an aqueous redox cell. [Figure 7] This is a cyclic voltammogram obtained when 2,2',6,6'-tetrabenzylamine-5,5'-dihydroxy-1,1'-dicarbonylbinaphthalene (a naphthoquinone-type compound) and 1,1',5,5'-tetrahydroxy-2,2',6,6'-tetrabenzylaminenaphthalene (a naphthol-type compound) were produced in an electrochemical reaction cell using 2,6-dibenzylamine-1,5-naphthodiol as a substrate in Example 5. Measurement conditions: graphite was used as the working electrode and counter electrode, and a saturated calomel electrode was used as the reference electrode, with a sweep rate of 50 mV / s. [Figure 8] This is a photograph of the actual cathode electrolyte used in producing 2,2',6,6'-tetrabenzylamine-5,5'-dihydroxy-1,1'-dicarbonylbinaphthalene (a naphthoquinone compound) in an electrochemical reaction cell using 2,6-dibenzylamine-1,5-naphthodiol as a substrate in Example 6. The suspension on the left is a 3 mol / L sulfuric acid solution of 0.1 mol / L 2,6-dibenzylamine-1,5-naphthodiol, and the clear liquid on the right is a 3 mol / L sulfuric acid solution of 2,2',6,6'-tetrabenzylamine-5,5'-dihydroxy-1,1'-dicarbonylbinaphthalene, the electrochemical oxidation product. [Figure 9]Current-voltage curves of a cycling stability test using 3,5,7-tribenzylamine-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminenaphthalene (a naphthol compound) as the positive electrode electrolyte in a flow cell. Test conditions: current density 40 mA cm-2, charge cut-off voltage 1.4 V, discharge cut-off voltage 0.1 V. [Figure 10] Stability curves for long-term cycling tests (under air conditions) using low concentrations of 3,5,7-tribenzylamine-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone-type compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminenaphthalene (a naphthol-type compound) as the positive electrode electrolyte in a flow cell. Test conditions: current density 40 mA cm-2, charge cut-off voltage 1.4 V, discharge cut-off voltage 0.1 V. [Figure 11] Stability curves for long-term cycling tests (under air conditions) using high-concentration 3,5,7-tribenzylamine-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone-type compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminenaphthalene (a naphthol-type compound) as the positive electrode electrolyte in a flow cell. Test conditions: current density 40 mA cm-2, charge cut-off voltage 1.4 V, discharge cut-off voltage 0.1 V. [Figure 12] Stability curves for a long-term cycling test (under air conditions) using a flow battery with high-concentration 3,5,7-tribenzylamine-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone-type compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminenaphthalene (a naphthol-type compound) as the positive electrode electrolyte and a vanadium electrolyte as the negative electrode. Test conditions: current density 40 mAcm-2, charge cut-off voltage 1.4 V, discharge cut-off voltage 0.1 V. [Figure 13]Charge / discharge curves for a cell stack consisting of 3,5,7-tribenzylamine-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminenaphthalene (a naphthol compound) as the positive electrode electrolyte and vanadium as the negative electrode electrolyte. Test conditions: current density 60.92mAcm-2, charge cut-off voltage 13V, discharge cut-off voltage 1V. [Figure 14] Cycle stability test results for a cell stack (under air conditions) configured with 3,5,7-tribenzylamine-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminenaphthalene (a naphthol compound) as the positive electrode electrolyte and vanadium as the negative electrode electrolyte. Test conditions: current density 60.92mAcm-2, charge cut-off voltage 13V, discharge cut-off voltage 1V. [Figure 15] Stability curves for a long-term cycling test (under air conditions) using 3-benzylamine-2-hydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone-type compound) and 1,2,3-trihydroxy-3-benzylaminenaphthalene (a naphthol-type compound) as the positive electrode electrolyte in a flow cell. Test conditions: current density 40 mA cm-2, charge cut-off voltage 1.4 V, discharge cut-off voltage 0.1 V. [Figure 16] Stability curves for a long-term cycling test (under air conditions) using 3,5,7-tribenzylamine-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone-type compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminenaphthalene (a naphthol-type compound) as the positive electrode electrolyte in a flow cell. Test conditions: current density 40 mA cm-2, charge cut-off voltage 1.4 V, discharge cut-off voltage 0.1 V. [Figure 17] 1H-NMR spectrum of the product obtained when 2,6-dihydroxynaphthalene was used as a starting material to produce 2,6-dibenzylamine-1,5-dihydroxynaphthalene (a naphthol compound) in Example 15. [Figure 18]This is a cyclic voltammogram obtained when 2,6-dibenzylamine-1,5-dihydroxynaphthalene (a naphthol compound) was used as the substrate in an electrochemical reaction cell to produce 2,6-dibenzylamine-1,5-dicarbonylnaphthalene (a naphthoquinone compound) in Example 15. Measurement conditions: graphite was used as the working electrode and counter electrode, and a saturated calomel electrode was used as the reference electrode, with a sweep rate of 50 mV / s. [Figure 19] Charge-discharge curves of an electrochemical oxidation-reduction test using 2,6-dibenzylamine-1,5-dicarbonylnaphthalene (a naphthoquinone compound) and 2,6-dibenzylamine-1,5-dihydroxynaphthalene (a naphthol compound) as the positive electrode electrolyte in a flow cell in Example 15. Test conditions: current density 80 mA cm, charge cut-off voltage 1.4 V, discharge cut-off voltage 0.1 V. [Figure 20] In Example 15, 2,6-dibenzylamine-1,5-dicarbonylnaphthalene (a naphthoquinone compound) and 2,6-dibenzylamine-1,5-dihydroxynaphthalene (a naphthol compound) were used as the positive electrode electrolyte in a flow battery. Test conditions: current density 80 mA cm-2, charge cut-off voltage 1.4 V, discharge cut-off voltage 0.1 V. DETAILED DESCRIPTION OF THE INVENTION

[0045] To more clearly illustrate the present invention, the following examples are presented based on experimental results and with reference to the drawings, but are not intended to limit the scope of the invention as defined in the claims.

[0046] Example 1 This example describes a process for producing 3-benzylamino-2-hydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) and 1,2,3-trihydroxy-3-benzylaminonaphthalene (a naphthol compound) using an electrochemical reaction cell. JPEG2026502426000019.jpg28170

[0047] Dissolve 2,4-dibenzylamino-1-naphthol in 3 mol / L sulfuric acid to prepare a 0.01 mol / L solution (50 mL). Transfer the solution to an electrochemical reaction cell and attach a graphite plate to the working electrode (1 cm 2 ) and counter electrode (4 cm 2 Using a saturated calomel electrode as the reference electrode, the potential was swept from low to high potential and then from high to low. The sweep range was 0 V to 1 V, the sweep rate was 50 mV / s, and 500 sweep cycles were performed. The naphthoquinone compound 3-benzylamino-2-hydroxy-1,4-dicarbonylnaphthalene was obtained at 0.25-0.30 V (vs. SCE), and the naphthol compound 1,2,3-trihydroxy-3-benzylaminonaphthalene was obtained at 0.15-0.2 V (vs. SCE). The product was successfully synthesized using mass spectrometry, proton nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy, with a yield of 60%. The starting material had a water solubility of less than 5 mM under acidic conditions, while the electrochemical oxidation product had a water solubility of approximately 1 M under acidic conditions.

[0048] 1 shows cyclic voltammograms obtained when 3-benzylamino-2-hydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone-type compound) and 1,2,3-trihydroxy-3-benzylaminonaphthalene (a naphthol-type compound) were produced in an electrochemical reaction cell using 2,4-dibenzylamino-1-naphthol as a raw material in Example 1. The measurement conditions were graphite as the working electrode and counter electrode, a saturated calomel electrode as the reference electrode, and a sweep rate of 50 mV / s.

[0049] <Example 2> This example describes a process for producing 3-benzylamino-2-hydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) and 1,2,3-trihydroxy-3-benzylaminonaphthalene (a naphthol compound) using an aqueous redox cell.

[0050] 2,4-Dibenzylamino-1-naphthol was dissolved in 3 mol / L sulfuric acid to prepare a 0.1 mol / L solution (20 mL) as the positive electrode electrolyte. Silicotungstic acid was dissolved in 3 mol / L sulfuric acid to prepare a 0.2 mol / L solution (20 mL) as the negative electrode electrolyte. An aqueous redox battery was assembled using a graphite plate as the current collector, graphite felt as the porous electrode, and polybenzimidazole as the diaphragm, and charged in constant current mode. The current density was 40 mAcm. -2 The charge cut-off voltage was set to 1.4 V, at which point the naphthoquinone compound 3-benzylamino-2-hydroxy-1,4-dicarbonylnaphthalene was obtained. The battery was then discharged in constant current mode at a current density of 40 mA cm. -2 The discharge cut-off voltage is set to 0.1 V, at which point the naphthol compound 1,2,3-trihydroxy-3-benzylaminonaphthalene is obtained. The product was confirmed to be successfully produced using evaluation methods such as mass spectrometry, proton nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy, with a yield of 72%. The raw material has a water solubility of less than 5 mM under acidic conditions, while the electrochemical oxidation product has a water solubility of approximately 1 M under acidic conditions.

[0051] 2 is an actual diagram of the positive electrode electrolyte used in producing 3-benzylamino-2-hydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) using 2,4-dibenzylamino-1-naphthol as a raw material in an aqueous redox cell in Example 2. The suspension on the left is a 3 mol / L sulfuric acid solution of 0.1 mol / L 2,4-dibenzylamino-1-naphthol, and the clear solution on the right is a 3 mol / L sulfuric acid solution of 3-benzylamino-2-hydroxy-1,4-dicarbonylnaphthalene, the electrochemical oxidation product.

[0052] Example 3 This example describes a process for producing 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminonaphthalene (a naphthol compound) using an electrochemical reaction cell. JPEG2026502426000020.jpg30170

[0053] Dissolve 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol in 3 mol / L sulfuric acid to prepare a 0.01 mol / L solution (50 mL). Transfer the solution to an electrochemical reaction cell and attach a graphite plate to the working electrode (1 cm 2 ) and counter electrode (4 cm 2 Using a saturated calomel electrode as the reference electrode, the potential was swept from low to high potential and then from high to low. The sweep range was 0 V to 1 V, the sweep rate was 50 mV / s, and 1000 sweep cycles were performed. At 0.32-0.35 V (vs. SCE), the naphthoquinone compound 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene was obtained, and at 0.25 V (vs. SCE), the naphthol compound 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminonaphthalene was obtained. The product was successfully synthesized using mass spectrometry, proton nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy, with a yield of 70%. The starting material had a water solubility of less than 1 M under acidic conditions, while the electrochemical oxidation product had a water solubility of approximately 1.6 M under acidic conditions.

[0054] 3 shows cyclic voltammograms obtained when 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone-type compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminonaphthalene (a naphthol-type compound) were produced in an electrochemical reaction cell using 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol as a raw material in Example 3. The measurement conditions were graphite as the working electrode and counter electrode, a saturated calomel electrode as the reference electrode, and a sweep rate of 50 mV / s.

[0055] Example 4 This example describes a process for producing 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminonaphthalene (a naphthol compound) using an aqueous redox cell.

[0056] 2,4,6,8-Tetrabenzylamino-1,5-naphthalenediol was dissolved in 3 mol / L sulfuric acid to prepare a 0.1 mol / L solution (20 mL) as the positive electrode electrolyte. Silicotungstic acid was dissolved in 3 mol / L sulfuric acid to prepare a 0.2 mol / L solution (20 mL) as the negative electrode electrolyte. An aqueous redox battery was assembled using a graphite plate as the current collector, graphite felt as the porous electrode, and polybenzimidazole as the diaphragm, and charged in constant current mode. The current density was 40 mAcm. -2 The charge cut-off voltage was set to 1.4 V, at which point the naphthoquinone compound 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene was obtained. The battery was then discharged in constant current mode at a current density of 40 mA cm. -2 The discharge cut-off voltage is set to 0.1 V, at which point the naphthol compound 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminonaphthalene is obtained. The product was successfully produced using evaluation methods such as mass spectrometry, proton nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy, with a yield of 92%. The raw material has a water solubility of less than 1 M under acidic conditions, while the electrochemical oxidation product has a water solubility of approximately 1.6 M under acidic conditions.

[0057] FIG. 4 shows characteristic molecular weights obtained by mass spectrometry of raw materials in the process of producing 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) using 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol as a raw material in an aqueous redox cell in Example 4.

[0058] FIG. 5 shows the characteristic molecular weight of 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene, an electrochemical oxidation product, obtained by mass spectrometry in the process of producing 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone-type compound) using 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol as a raw material in an aqueous redox cell in Example 4.

[0059] FIG. 6 shows the characteristic molecular weight of 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminonaphthalene obtained by mass spectrometry in the process of producing 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminonaphthalene (a naphthol-type compound) using 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol as a raw material in an aqueous redox cell in Example 4.

[0060] <Example 5> This example describes a process for producing 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminonaphthalene (a naphthol compound) using an electrochemical reaction cell. JPEG2026502426000021.jpg29170

[0061] Dissolve 2,6-dibenzylamino-1,5-naphthalenediol in 3 mol / L sulfuric acid to prepare a 0.01 mol / L solution (50 mL). Transfer the solution to an electrochemical reaction cell and attach a graphite plate to the working electrode (1 cm 2 ) and counter electrode (4 cm 2 Using a saturated calomel electrode as the reference electrode, the potential was swept from low to high potential and then from high to low. The sweep range was 0 V to 1 V, the sweep rate was 50 mV / s, and 500 sweep cycles were performed. The naphthoquinone compound 2,2',6,6'-tetrabenzylamino-5,5'-dihydroxy-1,1'-dicarbonylbinaphthalene was obtained at 0.23-0.24 V (vs. SCE), and the naphthol compound 1,1',5,5'-tetrahydroxy-2,2',6,6'-tetrabenzylaminonaphthalene was obtained at 0.21-0.22 V (vs. SCE). The product was successfully synthesized using mass spectrometry, proton nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy, with a yield of 70%. The starting material had a water solubility of less than 5 mM under acidic conditions, while the electrochemical oxidation product had a water solubility of approximately 2 M under acidic conditions.

[0062] 7 shows cyclic voltammograms obtained when 2,2',6,6'-tetrabenzylamino-5,5'-dihydroxy-1,1'-dicarbonylbinaphthalene (a naphthoquinone-type compound) and 1,1',5,5'-tetrahydroxy-2,2',6,6'-tetrabenzylaminonaphthalene (a naphthol-type compound) were produced in an electrochemical reaction cell using 2,6-dibenzylamino-1,5-naphthalenediol as a raw material in Example 5. The measurement conditions were graphite as the working electrode and counter electrode, a saturated calomel electrode as the reference electrode, and a sweep rate of 50 mV / s.

[0063] Example 6 This example describes a process for producing 2,2',6,6'-tetrabenzylamino-5,5'-dihydroxy-1,1'-dicarbonylbinaphthalene (a naphthoquinone compound) and 1,1',5,5'-tetrahydroxy-2,2',6,6'-tetrabenzylaminonaphthalene (a naphthol compound) using an aqueous redox cell.

[0064] 2,6-Dibenzylamino-1,5-naphthalenediol was dissolved in 3 mol / L sulfuric acid to prepare a 0.1 mol / L solution (20 mL) as the positive electrode electrolyte. Silicotungstic acid was dissolved in 3 mol / L sulfuric acid to prepare a 0.2 mol / L solution (20 mL) as the negative electrode electrolyte. An aqueous redox battery was assembled using a graphite plate as the current collector, graphite felt as the porous electrode, and polybenzimidazole as the diaphragm, and charged in constant current mode. The current density was 40 mAcm. -2 The charge cut-off voltage was set to 1.4 V, at which point the naphthoquinone compound 2,2',6,6'-tetrabenzylamino-5,5'-dihydroxy-1,1'-dicarbonylbinaphthalene was obtained. The battery was then discharged in constant current mode at a current density of 40 mA cm. -2The discharge cut-off voltage is set to 0.1 V, and the naphthol compound 1,1',5,5'-tetrahydroxy-2,2',6,6'-tetrabenzylaminonaphthalene is obtained. The product was confirmed to be successfully produced using evaluation methods such as mass spectrometry, proton nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy, with a yield of 70%. The water solubility of the raw material under acidic conditions is less than 5 mM, while the water solubility of the electrochemical oxidation product under acidic conditions is approximately 2 M.

[0065] 8 is an actual diagram of the positive electrode electrolyte used in producing 2,2',6,6'-tetrabenzylamino-5,5'-dihydroxy-1,1'-dicarbonylbinaphthalene (a naphthoquinone compound) in an electrochemical reaction cell using 2,6-dibenzylamino-1,5-naphthalenediol as a raw material in Example 6. The suspension on the left is a 3 mol / L sulfuric acid solution of 0.1 mol / L 2,6-dibenzylamino-1,5-naphthalenediol, and the clear solution on the right is a 3 mol / L sulfuric acid solution of 2,2',6,6'-tetrabenzylamino-5,5'-dihydroxy-1,1'-dicarbonylbinaphthalene, the electrochemical oxidation product.

[0066] Example 7 This example describes a process for constructing an aqueous redox storage battery using 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone-type compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminonaphthalene (a naphthol-type compound) as a redox couple at the positive electrode and ZnCl and Zn as a redox couple at the negative electrode.

[0067] The cathode electrolyte (10 mL) was 0.1 mol / L 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound), and the anode electrolyte (10 mL) was 0.2 mol / L zinc chloride solution, adjusted to pH 3 with sulfuric acid. An aqueous redox battery was assembled using a graphite plate as the current collector, graphite felt as the porous electrode, and polybenzimidazole as the diaphragm. The anode side was fitted with a 0.1 mm thick, 1 cm area battery. 2Discharge was performed in constant current mode with a current density of 10 mAcm. -2 The discharge cut-off voltage was set to 0.1 V, and the battery was subsequently charged in constant current mode at a current density of 10 mA cm -2 The charge cut-off voltage is set to 1.2 V. One redox process constitutes one charge / discharge cycle, and multiple charge / discharge cycles are possible, making such water-soluble naphthalene-type compounds promising for application in aqueous redox batteries.

[0068] Example 8 This example describes electrochemical redox tests using 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone-type compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminonaphthalene (a naphthol-type compound) as the positive electrode electrolyte in a flow cell. JPEG2026502426000022.jpg35170

[0069] The starting material for oxidized naphthoquinone and reduced naphthol is 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol, and the target product is obtained by electrochemical oxidation. The specific operation is as follows:

[0070] A 3.0 mol / L aqueous sulfuric acid solution was prepared, and the naphthol precursor, 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol, was dissolved in the sulfuric acid solution to prepare 20 mL of a 0.1 mol / L electrolyte. Next, silicotungstic acid hydrate was dissolved in the 3.0 mol / L sulfuric acid solution to obtain 80 mL of a 0.1 mol / L silicotungstic acid electrolyte. A flow battery was assembled using the resulting 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol and silicotungstic acid electrolyte, a graphite plate as a current collector, graphite felt as an electrode material, a polybenzimidazole ion-exchange membrane as a diaphragm, a tetrafluoroethylene resin flow frame, stainless steel end plates, and other components. 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol and silicotungstic acid electrolytes were used for the positive and negative electrodes of the flow cell, respectively. A peristaltic pump and milk tube were used to pump the electrolyte from the reservoir to the cell cavity and back, circulating the electrolyte to fully infiltrate the graphite felt. The cell was then subjected to a charge-discharge redox test, with a charge-discharge current of 1.92 A (current density 40 mA cm). -2 ) with end voltages of 1.4 V and 0.1 V, respectively. The stability of the battery was examined by cyclic charging and discharging, and the current-voltage curves around 330 hours of testing are shown in Figure 9. The battery operated stably during charging and discharging, and its capacity was also stably maintained. The structures of the corresponding oxidized and reduced forms of the naphthalene-type compounds could be determined by evaluation methods such as mass spectrometry, proton nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy.

[0071] Example 9 This example describes a process of conducting a long-term cycling electrochemical stability test using 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminonaphthalene (a naphthol compound) as the positive electrode electrolyte of a flow battery in combination with a silicotungstic acid negative electrode under low concentration conditions.

[0072] The starting material for oxidized naphthoquinone and reduced naphthol is 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol, and the target product is obtained by electrochemical oxidation. The specific operation is as follows:

[0073] A 3.0 mol / L aqueous sulfuric acid solution was prepared, and the naphthol precursor, 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol, was dissolved in the sulfuric acid solution to prepare 20 mL of a 0.1 mol / L electrolyte. Next, silicotungstic acid hydrate was dissolved in the 3.0 mol / L sulfuric acid solution to obtain 80 mL of a 0.1 mol / L silicotungstic acid electrolyte. A flow battery was assembled using the resulting 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol and silicotungstic acid electrolyte, a graphite plate as a current collector, graphite felt as an electrode material, a polybenzimidazole ion-exchange membrane as a diaphragm, a tetrafluoroethylene resin flow frame, stainless steel end plates, and other components. 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol and silicotungstic acid electrolytes were used for the positive and negative electrodes of the flow cell, respectively. A peristaltic pump and milk tube were used to pump the electrolyte from the reservoir to the cell cavity and back, circulating the electrolyte to fully infiltrate the graphite felt. The cell was then subjected to a charge-discharge redox test, with a charge-discharge current of 1.92 A (current density 40 mA cm). -2 ) with end voltages of 1.4 V and 0.1 V, respectively. A cycling stability test was performed on the battery, and as shown in Figure 10, the battery's charge / discharge capacity was maintained stably, with no significant capacity fluctuations or decay observed. The battery's coulombic efficiency was close to 100%, and its energy efficiency was stable at close to 70%. The structures of the corresponding oxidized and reduced forms of the naphthalene-type compounds could be determined using evaluation methods such as mass spectrometry, proton nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy.

[0074] Example 10 This example describes a process of conducting a long-term cycling electrochemical stability test using 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminonaphthalene (a naphthol compound) as the positive electrode electrolyte of a flow battery in combination with a silicotungstic acid negative electrode under high concentration conditions.

[0075] The starting material for oxidized naphthoquinone and reduced naphthol is 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol, and the target product is obtained by electrochemical oxidation. The specific operation is as follows:

[0076] A 3.0 mol / L aqueous sulfuric acid solution was prepared, and the naphthol precursor, 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol, was dissolved in the sulfuric acid solution to prepare 20 mL of a 1.5 mol / L electrolyte. Next, silicotungstic acid hydrate was dissolved in the 3.0 mol / L sulfuric acid solution to obtain 400 mL of a 0.3 mol / L silicotungstic acid electrolyte. A flow battery was assembled using the resulting 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol and silicotungstic acid electrolyte, a graphite plate as a current collector, graphite felt as an electrode material, a polybenzimidazole ion-exchange membrane as a diaphragm, a tetrafluoroethylene resin flow frame, stainless steel end plates, and other components. 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol and silicotungstic acid electrolytes were used for the positive and negative electrodes of the flow cell, respectively. A peristaltic pump and milk tube were used to pump the electrolyte from the reservoir to the cell cavity and back, circulating the electrolyte to fully infiltrate the graphite felt. The cell was then subjected to a charge-discharge redox test, with a charge-discharge current of 1.92 A (current density 40 mA cm). -2) with end voltages of 1.4 V and 0.1 V, respectively. A cycling stability test was performed on the battery, and as shown in Figure 11, the charge / discharge capacity of the battery was maintained stably, with no significant capacity fluctuation or decay observed. The battery's coulombic efficiency was nearly 100%, and the average energy efficiency was approximately 66%, demonstrating good cycling stability under high-concentration and atmospheric conditions. The structures of the corresponding oxidized and reduced forms of the naphthalene-type compounds can be determined by evaluation methods such as mass spectrometry, proton nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy.

[0077] Example 11 This example describes the process of conducting a long-term cycling electrochemical stability test using 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminonaphthalene (a naphthol compound) as the positive electrode electrolyte of a flow battery in combination with a vanadium negative electrode under high concentration conditions.

[0078] The starting material for oxidized naphthoquinone and reduced naphthol is 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol, and the target product is obtained by electrochemical oxidation. The specific operation is as follows:

[0079] A 3.0 mol / L aqueous sulfuric acid solution was prepared, and 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol, a naphthol precursor, was dissolved in the sulfuric acid solution to prepare a 1.0 mol / L cathode electrolyte. 3+ The resulting 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol and V 3+ An electrolyte solution was prepared, and a flow battery was assembled using graphite plates as current collectors, graphite felt as electrodes, a polybenzimidazole ion-exchange membrane as a diaphragm, a tetrafluoroethylene resin flow frame, stainless steel end plates, and other components. 3+Electrolytes were applied to the positive and negative electrodes of the flow cell, respectively, and a peristaltic pump and milk tube were used to pump the electrolyte from the reservoir to the cell cavity and back, circulating the electrolyte to fully infiltrate the graphite felt. The cell was then subjected to a charge-discharge redox test, with a charge-discharge current of 1.92 A (current density 40 mA cm). -2 ) with end voltages of 1.4 V and 0.1 V, respectively. A cycling stability test was performed on the battery, and as shown in Figure 12, the charge / discharge capacity of the battery was maintained stably, with no significant capacity fluctuation or decay observed. The battery's coulombic efficiency was nearly 100%, and the average energy efficiency was approximately 72%, demonstrating good cycling stability under high-concentration and atmospheric conditions. The structures of the corresponding oxidized and reduced forms of the naphthalene-type compounds can be determined by evaluation methods such as mass spectrometry, proton nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy.

[0080] Example 12 This example describes the process of conducting electrochemical oxidation-reduction and cycling stability tests using 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminonaphthalene (a naphthol compound) as the positive electrode electrolyte of a flow battery, enlarging the battery, using an electrode stack, and combining it with a vanadium negative electrode.

[0081] The starting material for oxidized naphthoquinone and reduced naphthol is 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol, and the target product is obtained by electrochemical oxidation. The specific operation is as follows:

[0082] A 3.0 mol / L aqueous sulfuric acid solution was prepared, and 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol, a naphthol precursor, was dissolved in the sulfuric acid solution to prepare 14 L of 0.6 mol / L cathode electrolyte. A 1 mol / L cathode electrolyte prepared with 3.0 mol / L sulfuric acid was used for the anode. 3+ The resulting 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol and V 3+An electrolyte was prepared, and a 10-cell 476cm2 battery was constructed using graphite plates as current collectors, graphite felt as electrode materials, and a polybenzimidazole ion-exchange membrane as a diaphragm. The battery was also equipped with a tetrafluoroethylene resin liquid flow frame and stainless steel end plates. 2 Assemble an electrode pile of 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol and V 3+ The electrolyte was applied to the positive and negative electrodes of the liquid flow battery, respectively. A magnetic pump and PP tubing were used to pump the electrolyte from the storage tank into the battery cavity and back, circulating the electrolyte to fully infiltrate the graphite felt. The battery was then subjected to a charge-discharge redox test, with a charge-discharge current of 29 A (current density 60.92 mA cm). -2 ) with end voltages of 13 V and 1 V, respectively. A cycling stability test of the pile was conducted, and the charge-discharge curves are shown in Figure 13. The figure indicates that the battery's charge-discharge curves are normal, demonstrating that the use of naphthalene-type compounds as the cathode electrolyte in a flow battery allows for large-scale operation. As shown in Figure 13, the charge-discharge capacity of the pile remained stable, with no significant capacity fluctuation or decay. The battery's coulombic efficiency was nearly 100%, and the average energy efficiency was approximately 58%, demonstrating good cycling stability under relatively high concentrations and atmospheric conditions. The strategy of using naphthalene-type compounds as the cathode of a flow battery was successfully scaled up and applied to a flow battery pile test system. The structures of the corresponding oxidized and reduced forms of the naphthalene-type compounds can be determined by various characterization methods, such as mass spectrometry, proton nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy.

[0083] Example 13 This example describes electrochemical redox and cycling stability tests using 3-benzylamino-2-hydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone-type compound) and 1,2,3-trihydroxy-3-benzylaminonaphthalene (a naphthol-type compound) as the positive electrode electrolyte in a flow cell. The reaction scheme is as follows: JPEG2026502426000023.jpg28170

[0084] The starting material for oxidized naphthoquinone and reduced naphthol is 2,4-dibenzylamino-1-naphthol, and the target product is obtained by electrochemical oxidation. The specific procedure is as follows:

[0085] A 3.0 mol / L aqueous sulfuric acid solution was prepared, and the naphthol precursor, 2,4-dibenzylamino-1-naphthol, was dissolved in the sulfuric acid solution to prepare a 0.1 mol / L electrolyte. Next, silicotungstic acid hydrate was dissolved in the 3.0 mol / L sulfuric acid solution to obtain a 0.1 mol / L silicotungstic acid electrolyte. The resulting 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol and silicotungstic acid electrolyte were prepared, and a flow battery was assembled using a graphite plate as a current collector, graphite felt as an electrode material, a polybenzimidazole ion-exchange membrane as a diaphragm, a tetrafluoroethylene resin flow frame, stainless steel end plates, and other components. 2,4-Dibenzylamino-1-naphthol and silicotungstic acid electrolytes were used for the positive and negative electrodes of the flow cell, respectively. A peristaltic pump and milk tube were used to pump the electrolyte from the reservoir to the cell cavity and back, circulating the electrolyte to fully infiltrate the graphite felt. The cell was then subjected to a charge-discharge redox test, with a charge-discharge current of 1.92 A (current density 40 mA cm). -2 ) with end voltages of 1.4 V and 0.1 V, respectively. Battery stability tests showed no significant capacity fluctuation or decay during 300 charge-discharge oxidation-reduction cycles. The battery's coulombic efficiency was nearly 100%, and its average energy efficiency reached 52%. The structures of the corresponding oxidized and reduced forms of the naphthalene-type compounds could be determined by evaluation methods such as mass spectrometry, proton nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy.

[0086] Example 14 This example describes electrochemical oxidation-reduction and cycling stability tests using 3,5,7-tribenzylamino-2,8-dihydroxy-1,4-dicarbonylnaphthalene (a naphthoquinone-type compound) and 1,2,4,8-tetrahydroxy-3,5,7-tribenzylaminonaphthalene (a naphthol-type compound) as the positive electrode electrolyte in a flow cell. The reaction scheme is as follows: JPEG2026502426000024.jpg39170

[0087] The starting material for oxidized naphthoquinone and reduced naphthol is 2,6-dibenzylamino-1,5-naphthalenediol, and the target product is obtained by electrochemical oxidation. The specific procedure is as follows:

[0088] A 3.0 mol / L aqueous sulfuric acid solution was prepared, and the naphthol precursor, 2,6-dibenzylamino-1,5-naphthalenediol, was dissolved in the sulfuric acid solution to prepare 20 mL of a 0.1 mol / L electrolyte. Next, silicotungstic acid hydrate was dissolved in the 3.0 mol / L sulfuric acid solution to obtain 80 mL of a 0.1 mol / L silicotungstic acid electrolyte. A flow battery was assembled using the resulting 2,4,6,8-tetrabenzylamino-1,5-naphthalenediol and silicotungstic acid electrolyte, a graphite plate as a current collector, graphite felt as an electrode material, a polybenzimidazole ion-exchange membrane as a diaphragm, a tetrafluoroethylene resin flow frame, stainless steel end plates, and other components. 2,6-dibenzylamino-1,5-naphthalenediol and silicotungstic acid electrolytes were used for the positive and negative electrodes of the flow cell, respectively. A peristaltic pump and milk tube were used to pump the electrolyte from the reservoir to the cell cavity and back, circulating the electrolyte to fully infiltrate the graphite felt. The cell was then subjected to a charge-discharge redox test, with a charge-discharge current of 1.92 A (current density 40 mA cm). -2) with end voltages of 1.4 V and 0.1 V, respectively. The stability of the battery was examined by cyclic charging and discharging, and no significant capacity fluctuation or decay was observed during 1,000 charge-discharge redox cycles. The battery's coulombic efficiency was nearly 100%, and its average energy efficiency reached 60%. This indicates that this naphthalene-type compound can achieve stable redox reactions under atmospheric conditions and has prospects for large-scale commercialization. The structures of the corresponding oxidized and reduced forms of the naphthalene-type compound can be determined by evaluation methods such as mass spectrometry, proton nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy.

[0089] Example 15 This example illustrates the process for producing 2,6-dibenzylamino-1,5-dicarbonylnaphthalene (a naphthoquinone compound) and 2,6-dibenzylamino-1,5-dihydroxynaphthalene (a naphthol compound). JPEG2026502426000025.jpg34170

[0090] 9.5 g of 2,6-naphthalenediol was dissolved in 100 mL of ethanol, followed by the addition of 36 mL of 36% aqueous formaldehyde solution and 70 mL of 40% aqueous dimethylamine solution, followed by a 20-hour reaction at 125°C. After cooling to room temperature, the solution was filtered and washed with ethanol to obtain white crystals, which were the target product, 2,6-dibenzylamino-1,5-dihydroxynaphthalene (a naphthol compound). The product was successfully synthesized using evaluation methods such as mass spectrometry, proton nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy, with an 86% yield. Furthermore, 2,6-dibenzylamino-1,5-dihydroxynaphthalene was dissolved in 3 mol / L sulfuric acid to prepare a 0.01 mol / L solution (50 mL). This solution was transferred to an electrochemical reaction cell, and a graphite plate was attached to the working electrode (1 cm). 2 ) and counter electrode (4 cm 2), and when the potential is swept from low to high using a saturated calomel electrode as the reference electrode, 2,6-dibenzylamino-1,5-dicarbonylnaphthalene (a naphthoquinone-type compound) is produced (sweep range 0V to 1V, sweep rate 50mV / s). Subsequently, when the potential is swept from high to low, 2,6-dibenzylamino-1,5-dihydroxynaphthalene (a naphthol-type compound) is produced (sweep range 1V to 0V, sweep rate 50mV / s).

[0091] Example 16 This example describes an electrochemical oxidation-reduction test using 2,6-dibenzylamino-1,5-dicarbonylnaphthalene (a naphthoquinone-type compound) and 2,6-dibenzylamino-1,5-dihydroxynaphthalene (a naphthol-type compound) as the positive electrode electrolyte in a flow cell. The reaction scheme is as follows: JPEG2026502426000026.jpg33170

[0092] The specific operations are as follows: A 3.0 mol / L aqueous sulfuric acid solution was prepared, and 2,6-dibenzylamino-1,5-dihydroxynaphthalene was dissolved in the sulfuric acid solution to prepare 7 mL of 0.1 mol / L electrolyte. Next, silicotungstic acid hydrate was dissolved in the 3.0 mol / L sulfuric acid solution to obtain 30 mL of 0.1 mol / L silicotungstic acid electrolyte. A flow battery was assembled using graphite plates as current collectors, graphite felt as electrodes, a polybenzimidazole ion-exchange membrane as a diaphragm, a tetrafluoroethylene flow frame, and stainless steel end plates. 2,6-dibenzylamino-1,5-dihydroxynaphthalene and silicotungstic acid electrolytes were used as the positive and negative electrodes, respectively. A peristaltic pump and milk tube were used to circulate the electrolyte from the storage tank to the battery cavity and back, thoroughly wetting the graphite felt. Next, a charge / discharge oxidation / reduction test was performed on the battery, and the charge / discharge current was set to 0.72 A (current density 80 mA cm -2) with end voltages of 1.4 V and 0.1 V, respectively. A charge-discharge test was performed on the assembled battery, and the current-voltage curve of the battery was recorded. As shown in Figure 19, the current-voltage curve of the battery was smooth and stable during continuous charge-discharge cycles. The structures of the corresponding oxidized and reduced naphthalene-type compounds can be determined by evaluation methods such as mass spectrometry, proton nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy. A cycling stability test was performed on the assembled battery, and as shown in Figure 20, the coulombic efficiency of the battery reached 96.5% and the capacity retention rate was 74.2% after 20 consecutive charge-discharge cycles. The structures of the corresponding oxidized and reduced naphthalene-type compounds can be determined by evaluation methods such as mass spectrometry, proton nuclear magnetic resonance spectroscopy, and ultraviolet spectroscopy.

[0093] Furthermore, the above are merely some examples and corresponding comparative examples of the present application, and do not limit the present application in any way. Although the present application has been described above with better examples, these examples are not used to limit the present application. Those skilled in the art will recognize that slight changes or modifications made using the above technical content within the scope of the technical solution of the present application are equivalent to equivalent examples, and all fall within the scope of the technical solution.

Claims

1. A naphthalene-type compound, the naphthalene-type compound includes a naphthoquinone-type compound and / or a naphthol-type compound, The naphthoquinone compound has any one of the structures represented by formula (1), formula (2), and formula (3), The naphthol compound is a naphthalene-type compound having any one of the structures represented by formula (4), formula (5), and formula (6). The naphthalene-type compounds having the structures represented by formula (1), formula (2), and formula (3) are oxidized naphthalene-type compounds, The naphthalene-type compounds having the structures represented by formula (4), formula (5), and formula (6) are reduced naphthalene-type compounds, an oxidized naphthalene compound having a structure represented by formula (1) and a reduced naphthalene compound having a structure represented by formula (4) form a pair of redox couples, an oxidized naphthalene compound having a structure represented by formula (2) and a reduced naphthalene compound having a structure represented by formula (5) form a pair of redox couples, an oxidized naphthalene compound having a structure represented by formula (3) and a reduced naphthalene compound having a structure represented by formula (6) form a pair of redox couples, R 11 , R 12 , R 21 , R 22 , R 31 , R 32 are independently H, F, Cl, Br, I, hydroxyl, methoxyl, carboxyl, sulfonic acid group, cyano group, -NR 2 , C 1 ~C 6 or C having a substituent X- 1 ~C 6 and is selected from the aliphatic groups C having the substituent X- 1 -C 6 A naphthalene-type compound, wherein the substituent X- in the aliphatic group is selected from the group consisting of carboxyl, sulfonic acid group, phosphonic acid group, hydroxyl, methoxyl, and trimethylamino.

2. 2. A method for producing the naphthalene-type compound of claim 1, comprising: It comprises the steps of: A production method comprising mixing a substrate and an acid, conducting electrochemical charging to obtain a naphthoquinone compound, and then conducting electrochemical discharging to obtain a naphthol compound.

3. The substrate has a structure represented by formula (7): R 11 , R 21 , R 31 , R 41 , R 12 , R 22 , R 32 , R 42 are independently H, F, Cl, Br, I, hydroxyl group, methoxy group, carboxyl group, sulfonic acid group, -NR 2 , C 1 -C 6 or a C1-C6 aliphatic group having a substituent X-, and R 11 , R 21 , R 31 , R 41 , R 12 , R 22 , R 32 , R 42 at least one of which is a hydroxyl group, 3. The method according to claim 2, wherein the substituent X- is any one of a carboxyl group, a sulfonic acid group, a phosphonic acid group, a hydroxyl group, a methoxy group, and a trimethylamino group.

4. the acid includes at least one of sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, citric acid, trifluoroacetic acid, and trifluoromethanesulfonic acid; 4. The method according to claim 2, wherein the concentration of the acid is 0.1 to 5 mol / L.

5. The method according to any one of claims 2 to 4, wherein the electrochemical charging and discharging steps are carried out in an electrochemical reaction cell or an aqueous battery.

6. When the electrochemical charging and discharging steps are carried out in an electrochemical reaction cell, A three-electrode system is used, with graphite plates as the working electrode and counter electrode, and the reference electrode is one of a silver-silver chloride electrode, a saturated calomel electrode, or a mercury-mercurous sulfate electrode. Scan rate: 5 to 500 mVs -1 and The voltage range is 0 to 1V. Electrochemical charge oxidation from low voltage to high voltage, followed by electrochemical discharge reduction from high voltage to low voltage; The charging voltage range is 0.23 to 0.35V (vs. SCE).

6. The method according to claim 5, wherein the discharge voltage range is 0.15 to 0.25 V (vs. SCE).

7. When the electrochemical charging and discharging steps are performed in an aqueous battery, the charging and discharging are performed in a constant current mode; The side containing the substrate and the acid is the positive electrode, and the negative electrode contains the conjugated redox compound; The conjugated redox compound is TiO 2+ / Ti 3+ , V 3+ / V 2+ or heteropolyacid, the heteropolyacid comprises silicotungstic acid; Current density is 1 to 120 mAcm -2 and The charge cut-off voltage is 1.2 to 1.4 V.

7. The method according to claim 5, wherein the discharge cut-off voltage is 0 to 0.1 V.

8. An aqueous redox storage battery, Contains an electrolyte, the electrolyte solution includes a positive electrode electrolyte solution and a negative electrode electrolyte solution, the positive electrode electrolyte contains a naphthoquinone-type compound in the naphthalene-type compound according to claim 1, or a naphthoquinone-type compound in the naphthalene-type compound produced by the production method according to any one of claims 2 to 7, and / or 8. An aqueous redox storage battery, wherein the negative electrode electrolyte contains a naphthol-type compound in the naphthalene-type compound according to claim 1, or a naphthol-type compound in the naphthalene-type compound produced by the production method according to any one of claims 2 to 7.

9. A liquid flow battery, Contains an electrolyte, the electrolyte solution includes a positive electrode electrolyte solution and a negative electrode electrolyte solution, the electrolyte solution contains a naphthalene-type compound; the naphthalene-type compound includes a naphthoquinone-type compound and / or a naphthol-type compound, the positive electrode electrolyte contains a naphthoquinone-type compound in the naphthalene-type compound, and the negative electrode electrolyte contains a naphthol-type compound in the naphthalene-type compound, Or, the positive electrode electrolyte contains a naphthol-type compound in the naphthalene-type compound, and the negative electrode electrolyte contains a naphthoquinone-type compound in the naphthalene-type compound, the concentration of the naphthalene-type compound in the positive electrode electrolyte or the negative electrode electrolyte is 0.01 to 3 mol / L; The naphthoquinone compound is a naphthoquinone compound in the naphthalene type compound according to claim 1, or a naphthoquinone compound in the naphthalene type compound produced by the production method according to any one of claims 2 to 7, A liquid flow battery characterized in that the naphthol compound is a naphthol compound in the naphthalene-type compound described in claim 1, or a naphthol compound in the naphthalene-type compound produced by the production method described in any one of claims 2 to 7.

10. 10. The flow battery according to claim 9, wherein the concentration of the naphthalene-type compound in the positive electrode electrolyte or the negative electrode electrolyte is 1.0 to 1.5 mol / L.

11. the positive electrode electrolyte or the negative electrode electrolyte further comprises a conjugated redox compound; The conjugated redox compound is TiO 2+ / Ti 3+ , V 3+ / V 2+ , and at least one heteropolyacid, 11. The flow battery according to claim 9, wherein the heteropolyacid comprises silicotungstic acid.

12. The electrolyte further contains an acid, the acid includes at least one of sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, citric acid, trifluoroacetic acid, and trifluoromethanesulfonic acid; 12. The flow battery according to claim 9, wherein the concentration of the acid is 0.01 to 6 mol / L.

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