WO2022042735A1 - 基于吩嗪衍生物的电解质及其在液流电池中的应用 - Google Patents

基于吩嗪衍生物的电解质及其在液流电池中的应用 Download PDF

Info

Publication number
WO2022042735A1
WO2022042735A1 PCT/CN2021/115459 CN2021115459W WO2022042735A1 WO 2022042735 A1 WO2022042735 A1 WO 2022042735A1 CN 2021115459 W CN2021115459 W CN 2021115459W WO 2022042735 A1 WO2022042735 A1 WO 2022042735A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
unsubstituted
substituted
formula
Prior art date
Application number
PCT/CN2021/115459
Other languages
English (en)
French (fr)
Inventor
王盼
季云龙
庞帅
徐健聪
王昕怡
Original Assignee
西湖大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN202110185442.8A external-priority patent/CN114105893A/zh
Application filed by 西湖大学 filed Critical 西湖大学
Publication of WO2022042735A1 publication Critical patent/WO2022042735A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
    • C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
    • C07D241/46—Phenazines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention belongs to the technical field of liquid flow battery energy storage. Specifically, it relates to the synthesis methods of several phenazine, quinone, phenothiazine and thien-type electrolytes of amino acid derivatives with redox activity, and their application in water-phase liquid flow battery energy storage system.
  • Existing large-scale energy storage technologies include pumped hydro energy storage, compressed air energy storage, electrochemical energy storage (secondary battery), supercapacitor energy storage, and flywheel energy storage.
  • the first three have long enough discharge times and large enough capacity ranges to store solar and wind energy.
  • Pumped hydro storage requires the establishment of two huge reservoirs at different altitudes. It is a large-scale project limited by special geographical conditions and may be accompanied by ecological problems, making it difficult to popularize in many places.
  • Compressed air energy storage is an energy storage method that uses electricity for compressed air, seals the compressed high-pressure air in the gas storage facility, and releases the compressed air to generate electricity when needed. Therefore, special geographical conditions such as rock caves, abandoned mines, etc.
  • flow batteries are divided into aqueous flow batteries and non-aqueous (organic solvent) flow batteries.
  • the organic solvent used in non-aqueous flow batteries has certain toxicity, and its cost is much higher than that of water, and may cause pollution to the environment; the safety hazards brought by the flammable and explosive nature of organic solvents also make non-aqueous liquid Flow batteries are not suitable for large-scale energy storage power stations. It can be seen that the aqueous flow battery has greater application prospects and application potential worthy of large-scale promotion.
  • the water-based flow battery using organic matter as energy storage material is a current research hotspot because of its wide source of energy storage materials and the possibility to modify and functionalize organic matter molecules by chemical means.
  • the purpose of the present invention is to develop a new type of organic energy storage material.
  • a first aspect of the present invention provides a compound represented by the following formula (I):
  • the dotted line is a chemical bond or does not exist
  • n1 and m2 are selected from the group consisting of 0, 1, 2, 3 or 4;
  • p1 and p2 are selected from the group consisting of 0, 1, 2, 3 or 4;
  • Each R is independently selected from the group consisting of halogen, substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, hydroxy, thiol group , amine group, carboxyl group, phosphoric acid group, sulfonic acid group or the following groups:
  • R 0 is selected from the group consisting of -COOX, -SO 3 X, -PO 3 H 2 , -NH 2 , -NHCH 3 , -N(CH 3 ) 2 , -N + (CH 3 ) 3 M - ; wherein, X is selected from the group consisting of H + , NH4 + , Li + , Na + , K + , Mg2+ , Al3 + , Ca2 + ; M is selected from the group consisting of F, Cl, Br or I; each Rg Each independently is a functionalized group; wherein, the functionalized group is in:
  • Ra and Rb are each independently selected from the group consisting of H, substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, or Ra and Rb together Form a substituted or unsubstituted 3-8 membered nitrogen-containing heterocycle or nitrogen-containing heteroaromatic ring; and at least one R 0 substituent is included on the Rg;
  • the substitution refers to the substitution of one or more hydrogen atoms on the group by a substituent selected from the group consisting of halogen, C1-C10 alkyl, cycloalkyl, heterocycloalkyl, C6 -C10 aryl group, hydroxyl group, thiol group, amine group, carboxyl group, phosphoric acid group, sulfonic acid group.
  • the compound has the structure shown in the following formula (Ia), formula (Ib), formula (Ic) or formula (Id):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from the group consisting of H, halogen, substituted or unsubstituted C1-C10 alkyl, cyclic Alkyl, heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, hydroxyl, thiol group, amine group, carboxyl group, phosphoric acid group, sulfonic acid group, or functionalized group;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 include at least one functional group.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from the group consisting of H, substituted or unsubstituted C1-C10 alkanes group, cycloalkyl, heterocycloalkyl, or functionalized group; wherein, the functionalized group is a group selected from the group consisting of:
  • each X, X 1 and X 2 are each independently selected from the group consisting of H, NH 4 + , Li + , Na + , K + , Mg 2+ , Al 3+ , Ca 2+ ;
  • R 9 , R 10 and R 11 are each independently selected from the group consisting of H, substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, or substituted or unsubstituted C6-C10 aryl ;
  • n 1, 2, 3, 4, 5, 6, 7 or 8;
  • C1 is a substituted or unsubstituted 3-8 membered heterocyclic ring (including partially unsaturated or saturated rings), or a substituted or unsubstituted 5-8 membered heteroaromatic ring.
  • said Ra and Rb are each independently selected from the following group: H, substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, and said Rg At least one R 0 substituent is included.
  • R 9 , R 10 and R 11 are each independently selected from the group consisting of H, substituted or unsubstituted C1-C10 alkyl, cycloalkyl, and heterocycloalkyl.
  • the compound is selected from the following group:
  • the second aspect of the present invention provides a method for preparing the compound according to the first aspect of the present invention, the method comprising the steps of:
  • M is F, Cl, Br or I.
  • the method in the step (i), is carried out in the presence of a palladium catalyst, a ligand and a base; preferably, the palladium catalyst is Pd 2 (dba) 3 , and the The base is tBuOK or Cs2CO3 , and the ligand is selected from the group consisting of BrettPhos , RuPhos, XPhos or Pd2(dba) 3 ;
  • the reaction is carried out in the presence of a palladium catalyst, a ligand, a base and a catalyst; preferably, the palladium catalyst is PdCl 2 , and the base It is potassium carbonate, the ligand is P(o-Tol) 3 , and the catalyst is Bu 4 NBr.
  • the reaction is carried out in the presence of palladium/carbon.
  • the reaction in the step (3), is carried out in the presence of an alkali; preferably, the alkali is NaOH.
  • the inert solvent is selected from the group consisting of tert-butanol, n-butanol, toluene, or a combination thereof.
  • the inert solvent is selected from the group consisting of DMF, water, or a combination thereof.
  • the inert solvent is selected from the following group: ethyl acetate.
  • the inert solvent is selected from the group consisting of methanol, water, or a combination thereof.
  • the method further includes: after the reaction is completed, filtering and collecting the filter cake, and the filter cake is dissolved in deionized water and then filtered again to remove water-insoluble impurities.
  • the method further includes: after the reaction is completed, purifying the product with a reversed-phase column.
  • a third aspect of the present invention provides a flow battery energy storage material, characterized in that the flow battery energy storage material is prepared by using the compound described in the first aspect of the present invention as an active ingredient.
  • a flow battery in a fourth aspect of the present invention, includes the compound according to the first aspect of the present invention as an energy storage material.
  • the compound according to the first aspect of the present invention is used as a negative electrode or a positive electrode solution.
  • Fig. 1 is the 1 H NMR chart of compound 3;
  • Figure 2 is the 13 C NMR chart of compound 3
  • Figure 3 is the 1 H NMR chart of compound 5;
  • Figure 4 is the 13 C NMR chart of compound 5;
  • Figure 5 is the 1 H NMR chart of compound 7
  • Figure 6 is the 13 C NMR chart of compound 7;
  • Figure 7 is the 1 H NMR chart of compound 9
  • Figure 8 is the 13 C NMR chart of compound 9
  • Figure 9 is the 1 H NMR chart of compound 11;
  • Figure 10 is the 13 C NMR chart of compound 11;
  • Figure 11 is the 1 H NMR chart of compound 13;
  • Figure 12 is the 13 C NMR chart of compound 13;
  • Figure 13 is the 1 H NMR chart of compound 14;
  • Figure 14 is the 13 C NMR chart of compound 14;
  • Figure 15 is the 1 H NMR chart of compound 15;
  • Figure 16 is the 13 C NMR chart of compound 15;
  • Figure 17 is the 1 H NMR chart of compound 16
  • Figure 18 is the 13 C NMR chart of compound 16
  • Figure 19 is the 1 H NMR chart of compound 19
  • Figure 20 is the 1 H NMR chart of compound 20
  • Figure 21 is the 1 H NMR chart of compound 21
  • Figure 22 is the 1 H NMR chart of compound 22
  • Figure 23 is the cyclic voltammogram of compound 15 in 1M KCl solution
  • Figure 24 is the main parameters and schematic diagram of the flow battery device
  • Figure 25 is a schematic diagram showing the variation of battery capacity, current efficiency and energy efficiency with the number of battery cycles of compound 15 as an energy storage material;
  • Figure 26 shows a schematic diagram of the relationship between battery capacity and voltage change under different cycles of battery cycles when compound 15 is used as an energy storage material
  • Figure 27 is the cyclic voltammogram of compound 3 in 1M KCl solution
  • Figure 28 is the cyclic voltammogram of compound 5 in 1M KCl solution
  • Figure 29 is the cyclic voltammogram of compound 7 in 1M KCl solution
  • Figure 30 is the cyclic voltammogram of compound 9 in 1M KCl solution
  • Figure 31 is the cyclic voltammogram of compound 11 in 1M KCl solution
  • Figure 32 is the cyclic voltammogram of compound 13 in 1M KCl solution
  • Figure 33 is the cyclic voltammogram of compound 14 in 1M KCl solution
  • Figure 34 is the cyclic voltammogram of compound 16 in 1M KCl solution
  • Figure 35 is the 1 H NMR chart of compound 22;
  • Figure 36 is the 1 H NMR chart of compound 23;
  • Figure 37 is the 1 H NMR chart of compound 24
  • Figure 38 is the 1 H NMR chart of compound 25
  • Figure 39 is the 1 H NMR chart of compound 26;
  • Figure 40 is the cyclic voltammogram of compound 21 in 1M KCl solution
  • Figure 41 is the cyclic voltammogram of compound 22 in 1M KCl solution
  • Figure 42 is the cyclic voltammogram of compound 23 in 1M KCl solution
  • Figure 43 is the cyclic voltammogram of compound 24 in 1M KCl solution
  • Figure 44 is the cyclic voltammogram of compound 25 in 1M KCl solution
  • Figure 45 is the cyclic voltammogram of compound 26 in 1M KCl solution
  • Figures 46 and 47 are the test results of the charge-discharge cycle of compound 22 in 1M KCl solution
  • Figures 48 and 49 are the test results of the charge-discharge cycle of compound 24 in 1M KCl solution
  • Figures 50 and 51 are the test results of the charge-discharge cycle of compound 25 in 1M KCl solution
  • Figures 52 and 53 are the test results of the charge-discharge cycle of compound 26 in 1M KCl solution
  • Figure 54 is the 1 H NMR chart of compound 27;
  • Figure 55 is a 13 C NMR chart of compound 27;
  • Figure 56 is the 1 H NMR chart of compound 28.
  • Figure 57 is the 13 C NMR chart of compound 28;
  • Figure 58 is the 1 H NMR chart of compound 29;
  • Figure 59 is the 13 C NMR chart of compound 29.
  • Figure 60 is the 1 H NMR chart of compound 30
  • Figure 61 is a 13 C NMR chart of compound 30;
  • Figure 62 is the 1 H NMR chart of compound 31;
  • Figure 63 is the 13 C NMR chart of compound 31;
  • Figure 64 is the 1 H NMR chart of compound 32
  • Figure 65 is a 13 C NMR chart of compound 32;
  • Figure 66 is the 1 H NMR chart of compound 33;
  • Figure 67 is the 13 C NMR chart of compound 33;
  • Figure 68 is the 1 H NMR chart of compound 34;
  • Figure 69 is the 13 C NMR chart of compound 34;
  • Figure 70 is the 1 H NMR chart of compound 35;
  • Figure 71 is the 13 C NMR chart of compound 35;
  • Figure 72 is a cyclic voltammogram of compound 27 in 1M H 2 SO 4 solution
  • Figure 73 is a cyclic voltammogram of compound 28 in 1M H 2 SO 4 solution
  • Figure 74 is a cyclic voltammogram of compound 29 in 1M H 2 SO 4 solution
  • Figure 75 is a cyclic voltammogram of compound 31 in 1M H 2 SO 4 solution
  • Figure 76 is a cyclic voltammogram of compound 32 in 1M H 2 SO 4 solution
  • Figure 77 is the test result of charge-discharge cycle of compound 27 in 1M KCl solution
  • Figure 78 is the test result of charge-discharge cycle of compound 29 in 1M KCl solution
  • Figures 79 and 80 are the test results of the charge-discharge cycle of compound 32 in 1M KCl solution
  • Figures 81 and 82 are the test results of the charge-discharge cycle of compound 35 in 1M KCl solution.
  • the present inventor After long-term and in-depth research, the present inventor has developed a compound that can be used as an energy storage material for an aqueous flow battery.
  • the compound preparation method is simple, and the prepared battery energy storage material has good cycle stability and energy efficiency. Based on the above findings, the inventors have completed the present invention.
  • the halogen is F, Cl, Br or I.
  • C1-C10 means having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms
  • C3-C6 means having 3, 4, 5 or 6 carbon atoms, and so on.
  • alkyl refers to a saturated linear or branched hydrocarbon moiety
  • C1-C10 alkyl refers to a straight or branched chain alkyl group having 1 to 10 carbon atoms, without limitation include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl, etc.; preferably ethyl, propyl, isopropyl, butyl , isobutyl, sec-butyl and tert-butyl.
  • aryl or "aromatic ring” refers to a hydrocarbyl moiety comprising one or more aromatic rings.
  • aryl groups include, but are not limited to, phenyl (Ph), naphthyl, pyrenyl, fluorenyl, anthracenyl, and phenanthryl.
  • heteroaryl refers to a moiety comprising one or more aromatic rings having at least one heteroatom (eg, N, O or S).
  • heteroaryl groups include furyl, pyrrolyl, thienyl, oxazolyl, imidazolyl, thiazolyl, pyridyl, pyrimidinyl, quinazolinyl, quinolinyl, isoquinolinyl, indolyl, and the like.
  • the positive and negative electrolytes are stored in an external storage tank, and transferred to the stack through a peristaltic pump.
  • the active material undergoes a redox reaction on the electrode surface to store and release energy.
  • flow batteries have the advantage that energy and power are independent of each other, that is, the energy depends on the concentration and volume of the energy storage material, while the power depends on the electrode area.
  • the cost of this technology is closer to the cost of energy storage materials, so although lithium-ion batteries have a higher energy density, flow batteries are more suitable for large-scale energy storage power stations.
  • solvent used in the electrolyte flow batteries are divided into aqueous flow batteries and non-aqueous (organic solvent) flow batteries.
  • Aqueous flow batteries are divided into aqueous inorganic flow batteries and aqueous organic flow batteries according to whether the energy storage material used is inorganic or organic.
  • the most studied and widely used energy storage materials are inorganic materials.
  • inorganic materials have high cost, limited resources, easy to form dendrites during use, and slow electrochemical reaction rates. scale application.
  • Using organic matter as an energy storage material has a wider source than metals with limited storage in the earth's crust, is cheaper to use, and can reduce the pollution of heavy metals to the environment.
  • organic materials Compared with inorganic materials, organic materials have the advantages of light weight, low price, ductility and plasticity; the electrochemical reaction speed of organic materials is faster, usually 1-2 orders of magnitude higher than that of inorganic metals, without the use of catalysts, nor will it form The dendrite destroys the separator; at the same time, synthetic chemists can modify and functionalize it at the molecular level, and optimize the solubility and redox potential of organic materials by introducing functional groups, thereby adjusting the energy density and open circuit voltage of the battery.
  • a compound that can be used as an organic energy storage material for an aqueous flow battery is provided.
  • the compound has the structure shown in the following formula (I):
  • the dotted line is a chemical bond or does not exist
  • n1 and m2 are selected from the group consisting of 0, 1, 2, 3 or 4;
  • p1 and p2 are selected from the group consisting of 0, 1, 2, 3 or 4;
  • Each R is independently selected from the group consisting of halogen, substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, hydroxy, thiol group , amine group, carboxyl group, phosphoric acid group, sulfonic acid group or the following groups:
  • R 0 is selected from the group consisting of -COOX, -SO 3 X, -PO 3 H 2 , -NH 2 , -NHCH 3 , -N(CH 3 ) 2 , -N + (CH 3 ) 3 M - ; wherein, X is selected from the group consisting of H + , NH4 + , Li + , Na + , K + , Mg2+ , Al3 + , Ca2 + ; M is selected from the group consisting of F, Cl, Br or I; each Rg Each independently is a functionalized group; wherein, the functionalized group is in:
  • Ra and Rb are each independently selected from the group consisting of H, substituted or unsubstituted C1-C10 alkyl, cycloalkyl, heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, or Ra and Rb together
  • a substituted or unsubstituted 3-8 membered nitrogen-containing heterocycle or nitrogen-containing heteroaromatic ring is formed; and the Rg at least includes one R 0 substituent.
  • the compound has the structure shown for each compound prepared in the Examples.
  • the compound is dissolved in a solvent and used as a negative electrode or a positive electrode solution for assembling a flow battery.
  • NMR spectra (including hydrogen and carbon spectra) of each of the above compounds are shown in Figures 1-18.
  • Compound 20-22 is obtained by the above method, and its nuclear magnetic spectrum is shown in Fig. 20-22.
  • the pure compound b (4.4 g, 11.6 mmol) prepared in the previous step was dissolved in 25 mL of methanol, and an aqueous sodium hydroxide solution [sodium hydroxide (9.28 g, 232 mmol) was dissolved in 25 mL of water] was added thereto, and the system was fully The reaction was carried out with stirring and the temperature was raised to 65°C. After reacting for 12 h, it was cooled to room temperature, and the reaction system was acidified with hydrochloric acid until a large amount of yellow-green solid was precipitated. The filter cake was then collected by filtration and thoroughly washed with distilled water, and the target compound 24 (3.72 g) was obtained after drying with a yield of 99%.
  • the crude product (2.87 g, 12.23 mmol) and palladium/carbon (290 mg) were weighed into a reaction flask, and the air in the reaction flask was replaced with nitrogen, and then with hydrogen. 21 mL of EtOH/H 2 O mixed solvent (v/v, 2:1) was added to the system, and the reaction was stirred at 100 degrees under a hydrogen atmosphere for 12 h. After the reaction was completed, it was cooled to room temperature, and Pd/C was filtered off to obtain a clear yellow solution, which was concentrated under reduced pressure and purified by C18 silica gel to obtain the target product 32 with an isolated yield of 87%.
  • Cyclic voltammetry testing uses a three-electrode system.
  • the working electrode is a 5mm glassy carbon electrode
  • the reference electrode is an aqueous Ag/AgCl electrode
  • the counter electrode is a platinum wire electrode.
  • the voltage scanning range during the test is -1.1V ⁇ -0.3V, and the scanning rate is 20mV/s.
  • test compound 15 in 1M KCl solution is shown in FIG. 23 .
  • the main parameters and schematic diagram of the flow battery device are shown in FIG. 24 .
  • the constant-current charge-discharge cycle test was performed using an electrochemical workstation.
  • the battery was assembled with compound 15, and Nafion117 cation exchange membrane and SGL39AA carbon paper were used as electrode materials.
  • the charge-discharge current was 100 mA, and the current density was 20 mA/cm 2 .
  • the anode solution was 6.9 mL of 0.1 M compound 15 dissolved in 1 M KCl solution; the cathode solution was 40 mL of 0.1 M K 4 FeCN 6 and 0.02 M K 3 FeCN 6 dissolved in 1 M KCl solution.
  • the cycling process adopts a constant current cycle with a current density of 20 mA/cm 2 .
  • test results of compound 15 in 1M KCl solution are shown in Figures 25 and 26.
  • the test results show that the compound has excellent battery cycle stability.
  • the constant current uninterrupted charge and discharge test for 6d has maintained a stable charge and discharge platform during the process, and the battery capacity has no decay.
  • the actual capacity accounts for 91% of the theoretical capacity. Energy efficiency up to 73%.
  • the research results fully show that these compounds are ideal energy storage materials for aqueous flow batteries.
  • the cyclic voltammogram of test compound 3 in 1M KCl solution is shown in FIG. 27 .
  • the cyclic voltammogram of test compound 5 in 1M KCl solution is shown in FIG. 28 .
  • the cyclic voltammogram of test compound 7 in 1M KCl solution is shown in FIG. 29 .
  • the cyclic voltammogram of test compound 9 in 1M KCl solution is shown in FIG. 30 .
  • the cyclic voltammogram of test compound 11 in 1M KCl solution is shown in FIG. 31 .
  • the cyclic voltammogram of test compound 13 in 1M KCl solution is shown in FIG. 32 .
  • the cyclic voltammogram of test compound 14 in 1M KCl solution is shown in FIG. 33 .
  • the cyclic voltammogram of test compound 16 in 1M KCl solution is shown in FIG. 34 .
  • the cyclic voltammogram of test compound 21 in 1M KCl solution is shown in FIG. 40 .
  • the cyclic voltammogram of test compound 22 in 1M KCl solution is shown in FIG. 41 .
  • the cyclic voltammogram of test compound 23 in 1M KCl solution is shown in FIG. 42 .
  • test compound 24 in 1M KOH solution is shown in FIG. 43 .
  • test compound 25 in 1M KOH solution is shown in FIG. 44 .
  • test compound 25 in 1M KOH solution is shown in FIG. 45 .
  • the main parameters and schematic diagram of the flow battery device are shown in FIG. 24 .
  • the constant-current charge-discharge cycle test was performed using an electrochemical workstation.
  • the battery was assembled with compound 22, and Nafion117 cation exchange membrane and SGL39AA carbon paper were used as electrode materials.
  • the charge-discharge current was 100 mA, and the current density was 20 mA/cm 2 .
  • the cycling process adopts a constant current cycle with a current density of 20 mA/cm 2 .
  • the test results show that the compound has excellent battery cycle stability.
  • the constant current uninterrupted charge and discharge test lasted for 10 days. During the process, it maintained a stable charge and discharge platform.
  • the battery capacity decayed by 0.61%/day. 88% capacity and 68% energy efficiency.
  • the research results fully show that these compounds are ideal energy storage materials for aqueous flow batteries.
  • the main parameters and schematic diagram of the flow battery device are shown in FIG. 24 .
  • Constant-current and constant-voltage charge-discharge cycle tests were performed using an electrochemical workstation.
  • the battery was assembled with compound 24, and Nafion117 cation exchange membrane and SGL39AA carbon paper were used as electrode materials.
  • the charge-discharge current was 100 mA, and the current density was 20 mA/cm 2 .
  • the cycle process adopts constant current and constant voltage cycle, and its current density is 20 mA/cm 2 .
  • the test results show that the compound has excellent battery cycle stability.
  • the constant current and constant voltage uninterrupted charge and discharge test for a total of 20 days has maintained a stable charge and discharge platform during the process.
  • the battery capacity decays by 0.0033%/day, and the actual capacity
  • the performance accounts for 96% of the theoretical capacity, and the energy efficiency reaches 66%.
  • the research results fully show that these compounds are ideal energy storage materials for aqueous flow batteries.
  • the main parameters and schematic diagram of the flow battery device are shown in FIG. 24 .
  • Constant-current and constant-voltage charge-discharge cycle tests were performed using an electrochemical workstation.
  • the battery was assembled with compound 25, and Nafion117 cation exchange membrane and SGL39AA carbon paper were used as electrode materials.
  • the charge-discharge current was 100 mA, and the current density was 20 mA/cm 2 .
  • the cycle process adopts constant current and constant voltage cycle, and its current density is 20 mA/cm 2 .
  • the test results show that the compound has excellent battery cycle stability.
  • the constant current and constant voltage uninterrupted charge-discharge test has a total of 20d, and has maintained a stable charge-discharge platform during the process.
  • the battery capacity decays by 0.0044%/day. It accounts for 99% of the theoretical capacity, and the energy efficiency reaches 65%.
  • the research results fully show that these compounds are ideal energy storage materials for aqueous flow batteries.
  • the main parameters and schematic diagram of the flow battery device are shown in FIG. 24 .
  • Constant-current and constant-voltage charge-discharge cycle tests were performed using an electrochemical workstation.
  • the battery was assembled with compound 26, and Nafion117 cation exchange membrane and SGL39AA carbon paper were used as electrode materials.
  • the charge-discharge current was 100 mA, and the current density was 20 mA/cm 2 .
  • the cycle process adopts constant current and constant voltage cycle, and its current density is 20 mA/cm 2 .
  • the test results show that the compound has excellent battery cycle stability.
  • the constant current and constant voltage uninterrupted charge-discharge test has a total of 18d, and has maintained a stable charge-discharge platform during the process.
  • the battery capacity decays by 0.1110%/day. It accounts for 96% of the theoretical capacity, and the energy efficiency reaches 70%.
  • the research results fully show that these compounds are ideal energy storage materials for aqueous flow batteries.
  • the main parameters and schematic diagram of the flow battery device are shown in FIG. 24 .
  • the constant-current charge-discharge cycle test was performed using an electrochemical workstation.
  • the battery was assembled with compound 27, and Nafion117 cation exchange membrane and SGL39AA carbon paper were used as electrode materials.
  • the charge-discharge current was 100 mA, and the current density was 20 mA/cm 2 .
  • the cycling process adopts a constant current cycle with a current density of 20 mA/cm 2 . Test temperature: 45°C.
  • the main parameters and schematic diagram of the flow battery device are shown in FIG. 24 .
  • the constant-current charge-discharge cycle test was performed using an electrochemical workstation.
  • the battery was assembled with compound 29, using Nafion117 cation exchange membrane and SGL39AA carbon paper as electrode materials.
  • the charge-discharge current was 100 mA, and the current density was 20 mA/cm 2 .
  • the cycling process adopts a constant current cycle with a current density of 20 mA/cm 2 .
  • the constant current and constant voltage uninterrupted charge and discharge test lasted for 11.3 days. During the process, a stable charge and discharge platform was maintained. The capacity of the constant current battery was attenuated by 4.98%/day, the actual capacity accounted for 78.7% of the theoretical capacity, and the energy efficiency reached 72%; The capacity of the constant voltage battery decays by 3.69%/day, the actual capacity accounts for 66% of the theoretical capacity, and the energy efficiency reaches 71%. The research results fully show that these compounds are ideal energy storage materials for aqueous flow batteries.
  • the main parameters and schematic diagram of the flow battery device are shown in FIG. 24 .
  • the constant-current charge-discharge cycle test was performed using an electrochemical workstation.
  • the battery was assembled with compound 32, and Nafion117 cation exchange membrane and SGL39AA carbon paper were used as electrode materials.
  • the charge-discharge current was 100 mA, and the current density was 20 mA/cm 2 .
  • the cycling process adopts a constant current cycle with a current density of 20 mA/cm 2 .
  • the main parameters and schematic diagram of the flow battery device are shown in FIG. 24 .
  • the constant-current charge-discharge cycle test was performed using an electrochemical workstation.
  • the battery was assembled with compound 35, and Nafion117 cation exchange membrane and SGL39AA carbon paper were used as electrode materials.
  • the charge-discharge current was 100 mA, and the current density was 20 mA/cm 2 .
  • the cycling process adopts a constant current cycle with a current density of 20 mA/cm 2 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)

Abstract

本发明提供了一种基于吩嗪衍生物的电解质及其在液流电池中的应用，具体地，本发明提供了一种如下式(I)所示的化合物，所述的化合物可以用于制备高性能的液流电池储能材料。

Description

基于吩嗪衍生物的电解质及其在液流电池中的应用 技术领域
本发明属于液流电池储能技术领域。具体涉及到几种具有氧化还原活性的氨基酸衍生物的吩嗪类、醌类、吩噻嗪类和噻嗯类电解质的合成方法，及其在水相液流电池储能系统中的应用。
背景技术
传统能源(例如石油和煤)的迅速消耗及其带来的严重环境污染，迫切地要求我们使用更清洁的能源从而减少对环境的污染。随着科学技术的发展，清洁能源如太阳能、风能的成本已经低于传统能源，然而这两种清洁能源具有强波动性和间歇性,对周围环境要求很高。但人类的日常生产活动对电能的需求却十分规律，因此清洁能源的间歇性与波动性阻碍了它们在电网中大规模的应用。这种供需矛盾，要求我们发展一种大规模的储能技术来调节用电的高峰与低谷，即用电低谷时储存能量，高峰时输出能量，为电网的稳定性提供支持和保障。通过这样的调节作用，减少资源的浪费，使清洁能源得到妥善的存储和利用，使其从低价值、计划外的能源转化为高价值、可靠的产品。
现有的大规模储能技术有抽水蓄能、压缩空气储能、电化学储能(二次电池)、超级电容器储能和飞轮储能等。在上述所有储能技术中，前三种储能技术放电时间足够长和容量范围足够大，可用于储存太阳能和风能。抽水蓄能需要在不同海拔上建立两个巨大的蓄水池，是受特殊地理条件限制的大型工程，并可能伴随生态问题，难以在多地推广。压缩空气储能是将电力用于压缩空气，将压缩后的高压空气密封在储气设施中，在需要时释放压缩空气发电的储能方式。因此也需要特殊的地理条件如岩石洞穴、废弃矿井等作为大型储气室，而且在空气压缩与释放的过程中，部分能量转化为热能，导致这项技术效率低下。相比之下，电化学储能因其环境友好、能量效率高、维护成本低、性质可调和不受地理条件限制等优点受到广泛地关注，其中液流电池由于其丰富的电解质储备选择，是液流电池中最有应用前景的储能方式之一。
根据电解液使用的溶剂类别，液流电池分为水系液流电池和非水系(有机溶剂)液流电池。非水系液流电池所使用的有机溶剂存在一定的毒性，其成本也远远高于水，并可能对环境造成污染；有机溶剂的易燃易爆性所带来的安全隐患也使得非水系液流电池不适用于大规模储能电站。由此可见，水系液流电池具有更大的应用前景和值得被大规模推广的应用潜力。其中，以有机物作为储能材料的水系液流电池，因其储能物质来源广泛、可利用化学手段对有机物分子进行修饰改造及功能化，是当前的研究热点。
综上所述，本领域迫切需要开发新型的有机储能材料。
发明内容
本发明的目的是开发一种新型的有机储能材料。
本发明的第一方面，提供了一种如下式(I)所示的化合物：
Figure PCTCN2021115459-appb-000001
其中，Y和Z各自独立地选自下组：N、NH、C＝O或S；
虚线为化学键或不存在；
m1和m2选自下组：0、1、2、3或4；
p1和p2选自下组：0、1、2、3或4；
各个R各自独立地选自下组：卤素、取代或未取代的C1-C10的烷基、环烷基、杂环烷基，取代或未取代的C6-C10芳基、羟基、硫醇基团、胺基、羧基、磷酸基、磺酸基或以下基团：
Figure PCTCN2021115459-appb-000002
R 0选自下组：-COOX、-SO 3X、-PO 3H 2、-NH 2、-NHCH 3、-N(CH 3) 2、-N +(CH 3) 3M -；其中，X选自下组：H +、NH 4 +、Li +、Na +、K +、Mg 2+、Al 3+、Ca 2+；M选自下组：F、Cl、Br或I；各个Rg各自独立地为功能化基团；其中，所述的功能化基团为
Figure PCTCN2021115459-appb-000003
其中：
Ra和Rb各自独立地选自下组：H、取代或未取代的C1-C10的烷基、环烷基、杂环烷基，取代或未取代的C6-C10芳基、或Ra和Rb共同形成取代或未取代的3-8元的含氮杂环或含氮杂芳环；且所述的Rg上至少包括一个R 0取代基；
除特别说明之处，所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素，C1-C10的烷基、环烷基、杂环烷基，C6-C10芳基、羟基、硫醇基团、胺基、羧基、磷酸基、磺酸基。
在另一优选例中，所述的化合物具有如下式(Ia)、式(Ib)、式(Ic)或式(Id)所示的结构：
Figure PCTCN2021115459-appb-000004
其中，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8各自独立地选自下组：H、卤素、取代或未取代的C1-C10的烷基、环烷基、杂环烷基，取代或未取代的C6-C10芳基、羟基、硫醇基团、胺基、羧基、磷酸基、磺酸基，或功能化基团；
限定条件是，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8中至少包括一个功能化基团。
在另一优选例中，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8各自独立地选自下组：H、取代或未取代的C1-C10的烷基、环烷基、杂环烷基，或功能化基团；其中，所述的功能化基团是选自下组的基团：
Figure PCTCN2021115459-appb-000005
其中，各个X、X 1和X 2各自独立地选自下组：H、NH 4 +、Li +、Na +、K +、Mg 2+、Al 3+、Ca 2+；
R 9、R 10和R 11各自独立地选自下组：H、取代或未取代的C1-C10的烷基、环烷基、杂环烷基，或取代或未取代的C6-C10芳基；
n为1、2、3、4、5、6、7或8；
C1为取代或未取代的3-8元的杂环(包括部分不饱和或饱和环)，或取代或未取代的5-8元的杂芳环。
在另一优选例中，所述的Ra和Rb各自独立地选自下组：H、取代或未取代的C1-C10的烷基、环烷基、杂环烷基，且所述的Rg上至少包括一个R 0取代基。
在另一优选例中，所述的R 9、R 10和R 11各自独立地选自下组：H、取代或未取代的C1-C10的烷基、环烷基、杂环烷基。
在另一优选例中，所述的化合物选自下组：
Figure PCTCN2021115459-appb-000006
Figure PCTCN2021115459-appb-000007
本发明的第二方面，提供了一种如本发明第一方面所述的化合物的制备方法，所述的方法包括步骤：
Figure PCTCN2021115459-appb-000008
(i)在惰性溶剂中，用式(II)化合物与RgH反应，得到式(I)化合物；
或所述的方法包括步骤：
Figure PCTCN2021115459-appb-000009
(1)在惰性溶剂中，用式(III)化合物与CH 2＝CHCOOEt反应，得到式(IIIa)化合物；
Figure PCTCN2021115459-appb-000010
(2)在氢气气氛下，对式(IIIa)化合物进行还原，得到式(IIIb)化合物；
Figure PCTCN2021115459-appb-000011
(3)对式(IIIb)化合物进行水解脱保护，得到式(I-1)化合物；
其中，M为F、Cl、Br或I。
在另一优选例中，所述的步骤(i)中，所述的方法在钯催化剂，配体和碱存在下进行；优选地，所述的钯催化剂为Pd 2(dba) 3，所述的碱为 tBuOK或Cs 2CO 3，且所述的配体选自下组：BrettPhos、RuPhos、XPhos或Pd 2(dba) 3；
在另一优选例中，所述的步骤(1)中，所述的反应在钯催化剂，配体、碱和催化剂存在下进行；优选地，所述的钯催化剂为PdCl 2，所述的碱为碳酸钾，所述的配体为P(o-Tol) 3，且所述的催化剂为Bu 4NBr。
在另一优选例中，所述的步骤(2)中，所述的反应在钯/碳存在下进行。
在另一优选例中，所述的步骤(3)中，所述的反应在碱存在下进行；较佳地，所述的碱为NaOH。
在另一优选例中，所述的步骤(i)中，所述的惰性溶剂选自下组：叔丁醇、正丁醇、甲苯，或其组合。
在另一优选例中，所述的步骤(1)中，所述的惰性溶剂选自下组：DMF、水，或其组合。
在另一优选例中，所述的步骤(2)中，所述的惰性溶剂选自下组：乙酸乙酯。
在另一优选例中，所述的步骤(2)中，所述的惰性溶剂选自下组：甲醇、水，或其组合。
在另一优选例中，所述方法还包括：在反应结束后，过滤并收集滤饼，滤饼用去离子水溶解后再次过滤以除去水中不溶杂质。收集滤液，滤液用HCl酸化至pH＝3～4，固体析出后过滤。
在另一优选例中，所述方法还包括：在反应结束后，用反相柱对于产物进行提 纯。
本发明的第三方面，提供了一种液流电池储能材料，其特征在于，所述的液流电池储能材料是用如本发明第一方面所述的化合物作为活性成分制备的。
本发明的第四方面，提供了一种液流电池，所述的液流电池包括如本发明第一方面所述的化合物作为储能材料。
在另一优选例中，所述的液流电池中，如本发明第一方面所述的化合物作为负极或正极溶液。
应理解，在本发明范围内中，本发明的上述各技术特征和在下文(如实施例)中具体描述的各技术特征之间都可以互相组合，从而构成新的或优选的技术方案。限于篇幅，在此不再一一累述。
附图说明
图1为化合物3的 1H NMR图；
图2为化合物3的 13C NMR图；
图3为化合物5的 1H NMR图；
图4为化合物5的 13C NMR图；
图5为化合物7的 1H NMR图；
图6为化合物7的 13C NMR图；
图7为化合物9的 1H NMR图；
图8为化合物9的 13C NMR图；
图9为化合物11的 1H NMR图；
图10为化合物11的 13C NMR图；
图11为化合物13的 1H NMR图；
图12为化合物13的 13C NMR图；
图13为化合物14的 1H NMR图；
图14为化合物14的 13C NMR图；
图15为化合物15的 1H NMR图；
图16为化合物15的 13C NMR图；
图17为化合物16的 1H NMR图；
图18为化合物16的 13C NMR图；
图19为化合物19的 1H NMR图；
图20为化合物20的 1H NMR图；
图21为化合物21的 1H NMR图；
图22为化合物22的 1H NMR图；
图23为化合物15在1M KCl溶液中的循环伏安图；
图24为液流电池装置主要参数及示意图；
图25为化合物15作为储能材料的电池容量，电流效率，能量效率随电池循环圈数变化示意图；
图26显示了化合物15作为储能材料的情况下，电池循环不同圈数下，电池容量与电压变化关系示意图；
图27为化合物3在1M KCl溶液中的循环伏安图；
图28为化合物5在1M KCl溶液中的循环伏安图；
图29为化合物7在1M KCl溶液中的循环伏安图；
图30为化合物9在1M KCl溶液中的循环伏安图；
图31为化合物11在1M KCl溶液中的循环伏安图；
图32为化合物13在1M KCl溶液中的循环伏安图；
图33为化合物14在1M KCl溶液中的循环伏安图；
图34为化合物16在1M KCl溶液中的循环伏安图；
图35为化合物22的 1H NMR图；
图36为化合物23的 1H NMR图；
图37为化合物24的 1H NMR图；
图38为化合物25的 1H NMR图
图39为化合物26的 1H NMR图；
图40为化合物21在1M KCl溶液中的循环伏安图；
图41为化合物22在1M KCl溶液中的循环伏安图；
图42为化合物23在1M KCl溶液中的循环伏安图；
图43为化合物24在1M KCl溶液中的循环伏安图；
图44为化合物25在1M KCl溶液中的循环伏安图；
图45为化合物26在1M KCl溶液中的循环伏安图；
图46和47为化合物22在1M KCl溶液中的充放电循环测试结果；
图48和49为化合物24在1M KCl溶液中的充放电循环测试结果；
图50和51为化合物25在1M KCl溶液中的充放电循环测试结果；
图52和53为化合物26在1M KCl溶液中的充放电循环测试结果；
图54为化合物27的 1H NMR图；
图55为化合物27的 13C NMR图；
图56为化合物28的 1H NMR图；
图57为化合物28的 13C NMR图；
图58为化合物29的 1H NMR图；
图59为化合物29的 13C NMR图；
图60为化合物30的 1H NMR图；
图61为化合物30的 13C NMR图；
图62为化合物31的 1H NMR图；
图63为化合物31的 13C NMR图；
图64为化合物32的 1H NMR图；
图65为化合物32的 13C NMR图；
图66为化合物33的 1H NMR图；
图67为化合物33的 13C NMR图；
图68为化合物34的 1H NMR图；
图69为化合物34的 13C NMR图；
图70为化合物35的 1H NMR图；
图71为化合物35的 13C NMR图；
图72为化合物27在1M H 2SO 4溶液中的循环伏安图；
图73为化合物28在1M H 2SO 4溶液中的循环伏安图；
图74为化合物29在1M H 2SO 4溶液中的循环伏安图；
图75为化合物31在1M H 2SO 4溶液中的循环伏安图；
图76为化合物32在1M H 2SO 4溶液中的循环伏安图；
图77为化合物27在1M KCl溶液中的充放电循环测试结果；
图78为化合物29在1M KCl溶液中的充放电循环测试结果；
图79和80为化合物32在1M KCl溶液中的充放电循环测试结果；
图81和82为化合物35在1M KCl溶液中的充放电循环测试结果。
具体实施方式
本发明人经过长期而深入的研究，开发了一种能够作为水系液流电池储能材料的化合物。所述的化合物制备方法简单，且制备得到的电池储能材料具有较好的循环稳定性和能量效率。基于上述发现，发明人完成了本发明。
术语
在本发明中，所述卤素为F、Cl、Br或I。
在本发明中，术语“C1-C10”是指具有1、2、3、4、5、6、7、8、9或10个碳原子，“C3-C6”是指具有3、4、5或6个碳原子，依此类推。
在本发明中，术语“烷基”表示饱和的线性或支链烃部分，例如术语“C1-C10烷基”是指具有1至10个碳原子的直链或支链烷基，非限制性地包括甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基和已基等；优选乙基、丙基、异丙基、丁基、异丁基、仲丁基和叔丁基。
在本发明中，术语“芳基”或“芳环”表示包含一个或多个芳环的烃基部分。芳基的例子包括但不限于苯基(Ph)、萘基、芘基、芴基、蒽基和菲基。
在本发明中，术语“杂芳基”表示包含一个或多个具有至少一个杂原子(例如N,O或S)的芳环的部分。杂芳基的例子包括呋喃基、吡咯基、噻吩基、噁唑基、咪唑基、噻唑基、吡啶基、嘧啶基、喹唑啉基、喹啉基、异喹啉基和吲哚基等。
液流电池
在液流电池中，正、负极电解液分别储存在外部的储液罐中，通过蠕动泵传送到电堆里，活性物质在电极表面发生氧化还原反应实现能量的储存与释放。与锂离子电池等传统化学电池相比，液流电池具有能量与功率相互独立的优点，即能量大小取决于储能材料的浓度和体积，而功率大小取决于电极面积。当储能规模越大时，这项技术的成本就越接近储能材料的成本，所以尽管锂离子电池具有更高的能量密度，液流电池则更加适合于大规模的储能电站。根据电解液使用的溶剂类别，液流电池分为水系液流电池和非水系(有机溶剂)液流电池。
水系液流电池根据使用的储能材料是无机物或有机物，分为水系无机液流电池和水系有机液流电池。目前研究最多、应用最广泛的储能材料均为无机材料，然而无机材料成本高、资源有限，在使用过程中容易形成枝晶，且电化学反应速率慢等缺点限制了无机液流电池的大规模应用。以有机物作为储能材料，其来源比地壳中储存有限的金属更加广泛，使用成本更低廉，更可以减少重金属对环境的污染。相对于无机材料，有机材料具有质轻、价廉、延展性及可塑性等优点；有机材料的电化学反应速度较快，通常比无机金属高1-2个数量级，无需使用催化剂，也不会形成枝晶破坏隔膜； 同时合成化学家可以从分子水平对其进行修饰改造及功能化，通过引入官能团来优化有机材料的溶解度和氧化还原电位，从而调节电池的能量密度和开路电压。因此，研究有机储能材料的结构特性、电化学特性及其可能的降解机理，从而提高水系有机液流电池的性能、能量密度和寿命，同时降低其成本，对于推动液流电池在储能领域的应用、减少环境污染与能源浪费，并且满足人类生产活动对电能的需求具有非常重要的意义。
液流电池储能材料
本发明中，提供了一种能够用作为水系液流电池的有机储能材料的化合物，具体地，该化合物具有如下式(I)所示的结构：
Figure PCTCN2021115459-appb-000012
其中，Y和Z各自独立地选自下组：N、NH、C＝O或S；
虚线为化学键或不存在；
m1和m2选自下组：0、1、2、3或4；
p1和p2选自下组：0、1、2、3或4；
各个R各自独立地选自下组：卤素、取代或未取代的C1-C10的烷基、环烷基、杂环烷基，取代或未取代的C6-C10芳基、羟基、硫醇基团、胺基、羧基、磷酸基、磺酸基或以下基团：
Figure PCTCN2021115459-appb-000013
R 0选自下组：-COOX、-SO 3X、-PO 3H 2、-NH 2、-NHCH 3、-N(CH 3) 2、-N +(CH 3) 3M -；其中，X选自下组：H +、NH 4 +、Li +、Na +、K +、Mg 2+、Al 3+、Ca 2+；M选自下组：F、Cl、Br或I；各个Rg各自独立地为功能化基团；其中，所述的功能化基团为
Figure PCTCN2021115459-appb-000014
其中：
Ra和Rb各自独立地选自下组：H、取代或未取代的C1-C10的烷基、环烷基、杂环烷基，取代或未取代的C6-C10芳基、或Ra和Rb共同形成取代或未取代的3-8元的含氮杂环或含氮杂芳环；且所述的Rg上至少包括一个R 0取代基。
在优选的实施方式中，该化合物具有如实施例中所制备的各个化合物所示的结构。
所述的化合物溶于溶剂后作为负极或正极溶液，用于组装液流电池。
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件。除非另外说明，否则百分比和份数按重量计算。
实施例1-9吩嗪类氨基酸衍生物的合成
Figure PCTCN2021115459-appb-000015
氮气氛围下，称取2,7-二溴吩嗪(3mmol,1.014g),甘氨酸(7.2mmol,0.54g),Pd 2(dba) 3(5mol％,137.4mg),BrettPhos(10mol％,161mg),叔丁醇钾(15mmol,1.68g),叔丁醇30mL于厚壁耐压反应管中。充分搅拌并升温至100℃，反应12h后冷却至室温。过滤并收集滤饼，滤饼用去离子水溶解后再次过滤以除去水中不溶杂质。收集滤液，滤液用HCl酸化至pH＝3～4，固体析出后过滤,收集滤饼，滤饼用去离子水洗涤(2×5mL),干燥后得到目标化合物3。进一步，通过反相柱(C18)提纯(MeOH:H 2O＝15:85),产率92％.
采用上述的通用方法1，通过替换反应原料，得到如下化合物5-16：
Figure PCTCN2021115459-appb-000016
Figure PCTCN2021115459-appb-000017
上述各个化合物的核磁谱图(包括氢谱和碳谱)如图1-图18所示。
实施例10吩嗪类丙氨酸衍生物的合成
Figure PCTCN2021115459-appb-000018
合成步骤如下：
氮气氛围下，称取2,7-二溴吩嗪(3mmol,1.014g),3,3'-亚胺二丙腈(12mmol,1.48g),Pd 2(dba) 3(5mol％,137.4mg),BrettPhos(10mol％,161mg),碳酸铯(21mmol,6.842g),叔丁醇10mL,于反应管中。充分搅拌并升温至100℃,反应12h后趁热过滤。固体依次用去离子水,EtOH洗涤之后于真空干燥箱干燥，得到化合物18。称取化合物18(1mmol,422mg)加入厚壁耐压瓶,加入NaOH(4mmol,160mg),去离子水4mL,充分搅拌并升温至150℃,反应12h后冷却过滤，收集固体。进一步，通过反相柱(C18)提纯(MeOH:H 2O＝5:95)，得到化合物19。产率90％。
实施例11-13蒽醌类氨基酸衍生物的合成
Figure PCTCN2021115459-appb-000019
氮气氛围下，称取2,6-二碘蒽醌(3mmol,1.38g),甘氨酸(9mmol,0.68g),Pd 2(dba) 3(5mol％,137.4mg),BrettPhos(10mol％,161mg),叔丁醇钾(15mmol,1.68g),叔丁醇30mL于厚壁耐压反应管中。充分搅拌并升温至120℃,反应12h后冷却至室温。过滤 并收集滤饼，滤饼用去离子水溶解后再次过滤以除去水中不溶杂质。收集滤液，滤液用HCl酸化至pH＝3～4，固体析出后过滤,收集滤饼，滤饼用去离子水洗涤(2*5mL),干燥后得到目标化合物21。
通过上述方法得到化合物20-22，其核磁谱图如图20-22所示。
Figure PCTCN2021115459-appb-000020
实施例14-17吩嗪类衍生物的合成
Figure PCTCN2021115459-appb-000021
氮气环境下分别称取1,8-二溴吩嗪(10g,29.8mmol),丙烯酸乙酯(17.9g,178.8mmol),氯化钯(106mg,0.596mmol),三(邻甲基苯基)磷(726mg,2.384mmol),四丁基溴化铵(1.92g,5.96mmol),碳酸钾(16.4g,119.2mmol),N,N-二甲基甲酰胺(8mL),水(80mL)于厚壁耐压反应管中,充分搅拌并升温至100℃反应12h。反应结束后体系冷却至室温，体系中深色不溶固体经减压过滤，蒸馏水及石油醚洗涤后，重新溶解于二氯甲烷中，并加入蒸馏水以及饱和食盐水洗涤。随后体系有机相经分离、无水硫酸钠干燥、过滤以及减压浓缩后进行快速硅胶色谱柱层析(展开剂：二氯甲烷/乙酸乙酯/三乙胺＝500/20/3)，并得到大量深绿色固体。深绿色固体经乙酸乙酯洗涤及过滤后制备得到纯的黄绿色产物a(11.9g)，产率为70.8％。
称取黄绿色固体a(4.6g,12.23mmol)及钯/碳(460mg)于反应瓶中，并将反应瓶中的空气置换成氮气，进而置换成氢气。随后150mL乙酸乙酯加入上述体系，并在氢气氛围下85度搅拌反应12h。反应完成并冷却至室温的体系经硅藻土过滤，减压浓缩以及硅胶色谱柱层析(展开剂：石油醚/乙酸乙酯/三乙胺＝400/100/3)后得到纯的目标化合物b(4.4g),产率为94.6％。
最后，将上一步制备所得的纯品化合物b(4.4g,11.6mmol)溶于25mL甲醇，并向其中加入氢氧化钠水溶液[氢氧化钠(9.28g,232mmol)溶于25mL水]，体系充分搅拌并升温至65℃进行反应。反应12h后冷却至室温，并用盐酸酸化反应体系直至大量黄绿色固体析出。随后通过过滤收集滤饼并用蒸馏水进行充分洗涤，干燥后得到目标化合物24(3.72g),产率为99％。
采用上述的通用方法，通过替换反应原料，得到如下化合物25，26：
Figure PCTCN2021115459-appb-000022
实施例18-19吩嗪类氨基磺酸衍生物的合成
Figure PCTCN2021115459-appb-000023
氮气氛围下，称取1,8-二碘吩嗪(3mmol,1.296g),牛磺酸(9mmol,1.13g),CuI(10mol％,57.1mg),Ligand(20mol％,197mg),氢氧化钾(18mmol,1.00g),DMSO 30mL,于厚壁耐压反应管中。充分搅拌并升温至80℃,反应12h后冷却至室温。向体系中加入大量DCM，有棕红色固体析出，过滤收集滤饼。将过滤所得固体溶于水再次过滤，收集滤液，减压蒸馏除水后得到一黑红色固体，将所得固体通过C18硅胶纯化，以87％产率得到目标化合物29。
采用上述的通用方法，通过替换反应原料，得到如下化合物27，28：
Figure PCTCN2021115459-appb-000024
实施例20-24吩嗪类磺酸衍生物的合成
Figure PCTCN2021115459-appb-000025
氮气环境下分别称取1,8-二溴吩嗪(5mmol,1.014g),乙烯基磺酸钠水溶液(约2.3M水溶液,12.5mmol,5.5mL),氯化钯(5mol％,0.25mmol,44mg),三(邻甲基苯基)磷(0.5mmol,304mg),三乙胺(20mmol,2.02g),N,N-二甲基甲酰胺(40mL)于厚壁耐压反应管中,充分搅拌并升温至100℃反应12h。反应结束后体系冷却至室温。向体系中加入少量EtOH(≈5mL)，充分搅拌均匀后向体系中继续加入大量DCM，有大量固体析出，过滤收集滤饼，滤饼干燥得一黄绿色粗产物。
称取粗产物(2.87g,12.23mmol)及钯/碳(290mg)于反应瓶中，并将反应瓶中的空气置换成氮气，进而置换成氢气。向体系中加入21mL EtOH/H 2O混合溶剂(v/v,2:1)，并氢气氛围下100度搅拌反应12h。反应完成后冷却至室温，过滤除Pd/C得一澄清黄色溶液，减压浓缩后通过C18硅胶纯化得到目标产物32，分离产率为87％。
采用上述的通用方法，通过替换反应原料，得到如下化合物30,31,33,34,35：
Figure PCTCN2021115459-appb-000026
Figure PCTCN2021115459-appb-000027
测试实施例
测试例1循环伏安法测试(化合物15)
循环伏安法测试采用三电极体系。其中，工作电极为5mm玻碳电极，参比电极为水相Ag/AgCl，对电极为铂丝电极。测试时电压扫描范围：-1.1V～-0.3V，扫描速率为20mV/s。
测试化合物15在1M KCl溶液中的循环伏安图，如图23所示。结果显示该化合物可在中性(KCl)条件下表现出较好的氧化还原性能。且具有较高的负电势，E 1/2＝-0.56V,ΔE＝341mV。
测试例2电流循环测试
液流电池装置主要参数及示意图如图24中所示。使用电化学工作站进行恒流充放循环测试。用化合物15组装电池，采用Nafion117阳离子交换膜，SGL39AA碳纸作为电极材料。充放电电流为100mA，电流密度为20mA/cm 2。
电池循环过程中，其负极溶液为6.9mL 0.1M化合物15溶解在1M KCl溶液中；正极溶液为40mL 0.1M K 4FeCN 6和0.02M K 3FeCN 6溶解在1M KCl溶液中。循环过程采用恒流循环，其电流密度为20mA/cm 2。
化合物15在1M KCl溶液中的测试结果如图25、26所示。测试结果显示，该化合物具有优异的电池循环稳定性，恒流无间断充放电测试6d，在过程中一直保持稳定的充放电平台，电池容量无衰减，实际容量发挥占理论容量91％，能量效率达73％。研究结果充分表明，该类化合物是理想的水系液流电池储能材料。
测试例3循环伏安法测试(化合物3)
测试化合物3在1M KCl溶液中的循环伏安图，如图27所示。结果显示该化合物可在中性(KCl)条件下表现出较好的氧化还原性能。且具有较高的负电势，E 1/2＝-0.52V,ΔE＝95mV。
测试例4循环伏安法测试(化合物5)
测试化合物5在1M KCl溶液中的循环伏安图，如图28所示。结果显示该化合物可在中性(KCl)条件下表现出较好的氧化还原性能。且具有较高的负电势，E 1/2＝-0.54V,ΔE＝276mV。
测试例5循环伏安法测试(化合物7)
测试化合物7在1M KCl溶液中的循环伏安图，如图29所示。结果显示该化合物 可在中性(KCl)条件下表现出较好的氧化还原性能。且具有较高的负电势，E 1/2＝-0.52V,ΔE＝115mV。
测试例6循环伏安法测试(化合物9)
测试化合物9在1M KCl溶液中的循环伏安图，如图30所示。结果显示该化合物可在中性(KCl)条件下表现出较好的氧化还原性能。且具有较高的负电势，E 1/2＝-0.53V,ΔE＝95mV。
测试例7循环伏安法测试(化合物11)
测试化合物11在1M KCl溶液中的循环伏安图，如图31所示。结果显示该化合物可在中性(KCl)条件下表现出较好的氧化还原性能。且具有较高的负电势，E 1/2＝-0.57V,ΔE＝205mV。
测试例8循环伏安法测试(化合物13)
测试化合物13在1M KCl溶液中的循环伏安图，如图32所示。结果显示该化合物可在中性(KCl)条件下表现出较好的氧化还原性能。且具有较高的负电势，E 1/2＝-0.52V,ΔE＝376mV。
测试例9循环伏安法测试(化合物14)
测试化合物14在1M KCl溶液中的循环伏安图，如图33所示。结果显示该化合物可在中性(KCl)条件下表现出较好的氧化还原性能。且具有较高的负电势，E 1/2＝-0.51V,ΔE＝425mV。
测试例10循环伏安法测试(化合物16)
测试化合物16在1M KCl溶液中的循环伏安图，如图34所示。结果显示该化合物可在中性(KCl)条件下表现出较好的氧化还原性能。且具有较高的负电势，E 1/2＝-0.51V,ΔE＝425mV。
测试例11循环伏安法测试(化合物21)
测试化合物21在1M KCl溶液中的循环伏安图，如图40所示。结果显示该化合物可在中性(KCl)条件下表现出较好的氧化还原性能。且具有较高的负电势，E 1/2＝-0.56V,ΔE＝44mV。
测试例12循环伏安法测试(化合物22)
测试化合物22在1M KCl溶液中的循环伏安图，如图41所示。结果显示该化合物可在中性(KCl)条件下表现出较好的氧化还原性能。且具有较高的负电势，E 1/2＝-0.60V,ΔE＝59mV。
测试例13循环伏安法测试(化合物23)
测试化合物23在1M KCl溶液中的循环伏安图，如图42所示。结果显示该化合物可在中性(KCl)条件下表现出较好的氧化还原性能。且具有较高的负电势，E 1/2＝-0.60V,ΔE＝48mV。
测试例14循环伏安法测试(化合物24)
测试化合物24在1M KOH溶液中的循环伏安图，如图43所示。结果显示该化合物可在碱性(KOH)条件下表现出较好的氧化还原性能。且具有较高的负电势，E 1/2＝-0.59V,ΔE＝163mV。
测试例15循环伏安法测试(化合物25)
测试化合物25在1M KOH溶液中的循环伏安图，如图44所示。结果显示该化合物可在碱性(KOH)条件下表现出较好的氧化还原性能。且具有较高的负电势，E 1/2＝-0.56V,ΔE＝195mV。
测试例16循环伏安法测试(化合物26)
测试化合物25在1M KOH溶液中的循环伏安图，如图45所示。结果显示该化合物可在碱性(KOH)条件下表现出较好的氧化还原性能。且具有较高的负电势，E 1/2＝-0.61V,ΔE＝91mV。
测试例17电流循环测试(化合物22)
Figure PCTCN2021115459-appb-000028
液流电池装置主要参数及示意图如图24中所示。使用电化学工作站进行恒流充放循环测试。用化合物22组装电池，采用Nafion117阳离子交换膜，SGL39AA碳纸作为电极材料。充放电电流为100mA，电流密度为20mA/cm 2。
电池循环过程中，其负极溶液为7.0mL 0.1M化合物22溶解在pH＝12的1M KCl溶液中；正极溶液为40mL 0.1M K 4FeCN 6和0.02M K 3FeCN 6溶解在pH＝12的1M KCl溶液中。循环过程采用恒流循环，其电流密度为20mA/cm 2。
化合物22在1M KCl(pH＝12)溶液中的测试结果如图46、47所示。测试结果显示，该化合物具有优异的电池循环稳定性，恒流无间断充放电测试总共10天，在过程中一直保持稳定的充放电平台，电池容量为衰减0.61％/day，实际容量发挥占理论容量88％，能量效率达68％。研究结果充分表明，该类化合物是理想的水系液流电池储能材料。
测试例18电流循环测试(化合物24)
Figure PCTCN2021115459-appb-000029
液流电池装置主要参数及示意图如图24中所示。使用电化学工作站进行恒流及恒压充放循环测试。用化合物24组装电池，采用Nafion117阳离子交换膜，SGL39AA碳纸作为电极材料。充放电电流为100mA，电流密度为20mA/cm 2。
电池循环过程中，其负极溶液为7.0mL 0.1M化合物24溶解在pH＝12的1M KCl溶液中；正极溶液为40mL 0.1M K 4FeCN 6和0.02M K 3FeCN 6溶解在pH＝12的1M KCl 溶液中。循环过程采用恒流与恒压循环，其电流密度为20mA/cm 2。
化合物24在1M KCl(pH＝12)溶液中的测试结果如图48、49所示。测试结果显示，该化合物具有优异的电池循环稳定性，恒流与恒压无间断充放电测试总共20天，在过程中一直保持稳定的充放电平台，电池容量为衰减0.0033％/day，实际容量发挥占理论容量96％，能量效率达66％。研究结果充分表明，该类化合物是理想的水系液流电池储能材料。
测试例19电流循环测试(化合物25)
Figure PCTCN2021115459-appb-000030
液流电池装置主要参数及示意图如图24中所示。使用电化学工作站进行恒流及恒压充放循环测试。用化合物25组装电池，采用Nafion117阳离子交换膜，SGL39AA碳纸作为电极材料。充放电电流为100mA，电流密度为20mA/cm 2。
电池循环过程中，其负极溶液为7.0mL 0.1M化合物25溶解在pH＝12的1M KCl溶液中；正极溶液为40mL 0.1M K 4FeCN 6和0.02M K 3FeCN 6溶解在pH＝12的1M KCl溶液中。循环过程采用恒流与恒压循环，其电流密度为20mA/cm 2。
化合物25在1M KCl(pH＝12)溶液中的测试结果如图50、51所示。测试结果显示，该化合物具有优异的电池循环稳定性，恒流与恒压无间断充放电测试总共20d，在过程中一直保持稳定的充放电平台，电池容量为衰减0.0044％/day，实际容量发挥占理论容量99％，能量效率达65％。研究结果充分表明，该类化合物是理想的水系液流电池储能材料。
测试例20电流循环测试(化合物26)
Figure PCTCN2021115459-appb-000031
液流电池装置主要参数及示意图如图24中所示。使用电化学工作站进行恒流及恒压充放循环测试。用化合物26组装电池，采用Nafion117阳离子交换膜，SGL39AA碳纸作为电极材料。充放电电流为100mA，电流密度为20mA/cm 2。
电池循环过程中，其负极溶液为7.0mL 0.1M化合物26溶解在pH＝12的1M KCl溶液中；正极溶液为40mL 0.1M K 4FeCN 6和0.02M K 3FeCN 6溶解在pH＝12的1M KCl溶液中。循环过程采用恒流与恒压循环，其电流密度为20mA/cm 2。
化合物26在1M KCl(pH＝12)溶液中的测试结果如图52、53所示。测试结果显示，该化合物具有优异的电池循环稳定性，恒流与恒压无间断充放电测试总共18d，在过程中一直保持稳定的充放电平台，电池容量为衰减0.1110％/day，实际容量发挥占理论容量96％，能量效率达70％。研究结果充分表明，该类化合物是理想的水系液流电池储能材料。
测试例21循环伏安法测试(化合物27-32)
测试化合物27-32在1M H 2SO 4溶液中的循环伏安图，如图72-76所示。结果显示该化合物可在酸性(H 2SO 4)条件下表现出较好的氧化还原性能。
化合物27：E 1/2＝0.186V,ΔE＝40mV
化合物28：E 1/2＝0.166V,ΔE＝51mV
化合物29：E 1/2＝0.178V,ΔE＝35mV
化合物31：E 1/2＝0.147V(VS.SHE),ΔE 1＝55mV(右),ΔE 2＝68mV(左)
化合物32：E 1/2＝0.148V(VS.SHE),ΔE 1＝58mV(右)，ΔE 2＝83mV(左)
测试例22电流循环测试(化合物27)
Figure PCTCN2021115459-appb-000032
液流电池装置主要参数及示意图如图24中所示。使用电化学工作站进行恒流充放循环测试。用化合物27组装电池，采用Nafion117阳离子交换膜，SGL39AA碳纸作为电极材料。充放电电流为100mA，电流密度为20mA/cm 2。
电池循环过程中，其负极溶液为7.0mL 0.1M化合物27溶解在pH＝12的1M KCl溶液中；正极溶液为40mL 0.1M K 4FeCN 6和0.02M K 3FeCN 6溶解在pH＝12的1M KCl溶液中。循环过程采用恒流循环，其电流密度为20mA/cm 2。测试温度：45℃。
化合物27在1M KCl(pH＝12)溶液中的测试结果如图77所示。研究结果充分表明，该类化合物是理想的水系液流电池储能材料。
恒流无间断充放电测试共3.3天，在过程中一直保持稳定的充放电平台，电池容量为衰减0.1104％/day，实际容量发挥占理论容量52％，能量效率达63％。研究结果充分表明，该类化合物是理想的水系液流电池储能材料。
测试例23电流循环测试(化合物29)
Figure PCTCN2021115459-appb-000033
液流电池装置主要参数及示意图如图24中所示。使用电化学工作站进行恒流充放循环测试。用化合物29组装电池，采用Nafion117阳离子交换膜，SGL39AA碳纸作为电极材料。充放电电流为100mA，电流密度为20mA/cm 2。
电池循环过程中，其负极溶液为7.0mL 0.1M化合物29溶解在pH＝12的1M KCl溶液中；正极溶液为40mL 0.1M K 4FeCN 6和0.02M K 3FeCN 6溶解在pH＝12的1M KCl溶液中。循环过程采用恒流循环，其电流密度为20mA/cm 2。
化合物29在1M KCl(pH＝12)溶液中的测试结果如图78所示。研究结果充分表明，该类化合物是理想的水系液流电池储能材料。
恒流恒压无间断充放电测试共11.3天，在过程中一直保持稳定的充放电平台，恒流电池容量为衰减4.98％/day，实际容量发挥占理论容量78.7％，能量效率达72％；恒压电池容量为衰减3.69％/day，实际容量发挥占理论容量66％，能量效率达71％。研究结果充分表明，该类化合物是理想的水系液流电池储能材料。
测试例24电流循环测试(化合物32)
Figure PCTCN2021115459-appb-000034
液流电池装置主要参数及示意图如图24中所示。使用电化学工作站进行恒流充放循环测试。用化合物32组装电池，采用Nafion117阳离子交换膜，SGL39AA碳纸作为电极材料。充放电电流为100mA，电流密度为20mA/cm 2。
电池循环过程中，其负极溶液为7.0mL 0.1M化合物32溶解在pH＝12的1M KCl溶液中；正极溶液为40mL 0.1M K 4FeCN 6和0.02M K 3FeCN 6溶解在pH＝12的1M KCl溶液中。循环过程采用恒流循环，其电流密度为20mA/cm 2。
化合物32在1M KCl(pH＝12)溶液中的测试结果如图79和80所示。研究结果充分表明，该类化合物是理想的水系液流电池储能材料。
恒流与恒压无间断充放电测试共21.3天，在过程中一直保持稳定的充放电平台，电池容量为衰减0.0061％/day，实际容量发挥占理论容量91.9％，能量效率达72％。研究结果充分表明，该类化合物是理想的水系液流电池储能材料。
测试例25电流循环测试(化合物35)
Figure PCTCN2021115459-appb-000035
液流电池装置主要参数及示意图如图24中所示。使用电化学工作站进行恒流充放循环测试。用化合物35组装电池，采用Nafion117阳离子交换膜，SGL39AA碳纸作为电极材料。充放电电流为100mA，电流密度为20mA/cm 2。
电池循环过程中，其负极溶液为7.0mL 0.1M化合物35溶解在pH＝12的1M KCl溶液中；正极溶液为40mL 0.1M K 4FeCN 6和0.02M K 3FeCN 6溶解在pH＝12的1M KCl溶液中。循环过程采用恒流循环，其电流密度为20mA/cm 2。
化合物35在1M KCl(pH＝12)溶液中的测试结果如图81和82所示。研究结果充分表明，该类化合物是理想的水系液流电池储能材料。
恒流与恒压无间断充放电测试共16天，在过程中一直保持稳定的充放电平台，电池容量无明显衰减，实际容量发挥占理论容量78.5％，能量效率达65％。研究结果充分表明，该类化合物是理想的水系液流电池储能材料。
上述各个实施例的结果显示，本发明的化合物用作为液流电池的储能材料时，具有较高的负电势和较好的氧化还原性能，因此是一种理想的水系液流电池储能材料。
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (10)

  1. 一种如下式(I)所示的化合物：
    Figure PCTCN2021115459-appb-100001
    其中，Y和Z各自独立地选自下组：N、NH、C＝O或S；
    虚线为化学键或不存在；
    m1和m2选自下组：0、1、2、3或4；
    p1和p2选自下组：0、1、2、3或4；
    各个R各自独立地选自下组：H、卤素、取代或未取代的C1-C10烷基、环烷基、杂环烷基，取代或未取代的C6-C10芳基、羟基、硫醇基团、胺基、羧基、磷酸基、磺酸基或以下基团：
    Figure PCTCN2021115459-appb-100002
    R 0选自下组：-COOX、-SO 3X、-PO 3H 2、-NH 2、-NHCH 3、-N(CH 3) 2、-N +(CH 3) 3M -；其中，X选自下组：H +、NH 4 +、Li +、Na +、K +、Mg 2+、Al 3+、Ca 2+；M选自下组：F、Cl、Br或I；各个Rg各自独立地为功能化基团或H；其中，所述的功能化基团为
    Figure PCTCN2021115459-appb-100003
    其中：
    Ra和Rb各自独立地选自下组：H，取代或未取代的C1-C10的烷基、环烷基、杂环烷基，取代或未取代的C6-C10芳基，或Ra和Rb共同形成取代或未取代的3-8元的含氮杂环或含氮杂芳环；且所述的Rg上至少包括一个R 0取代基；
    除特别说明之处，所述的取代指基团上的一个或多个氢原子被选自下组的取代基取代：卤素，C1-C10烷基、环烷基、杂环烷基，C6-C10芳基、羟基、硫醇基团、胺基、羧基、磷酸基、磺酸基。
  2. 如权利要求1所述的化合物，其特征在于，所述的化合物具有如下式(Ia)、式(Ib)、式(Ic)或式(Id)所示的结构：
    Figure PCTCN2021115459-appb-100004
    其中，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8各自独立地选自下组：H、卤素、取代或 未取代的C1-C10的烷基、环烷基、杂环烷基，取代或未取代的C6-C10芳基、羟基、硫醇基团、胺基、羧基、磷酸基、磺酸基，或功能化基团；
    限定条件是，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8中至少包括一个功能化基团。
  3. 如权利要求1所述的化合物，其特征在于，R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8各自独立地选自下组：H、取代或未取代的C1-C10的烷基、环烷基、杂环烷基，或功能化基团；其中，所述的功能化基团是选自下组的基团：
    Figure PCTCN2021115459-appb-100005
    其中，各个X、X 1和X 2各自独立地选自下组：H、NH 4 +、Li +、Na +、K +、Mg 2+、Al 3+、Ca 2+；
    R 9、R 10和R 11各自独立地选自下组：H、取代或未取代的C1-C10的烷基、环烷基、杂环烷基，或取代或未取代的C6-C10芳基；
    n为1、2、3、4、5、6、7或8；
    C1为取代或未取代的3-8元的杂环(包括部分不饱和或饱和环)，或取代或未取代的5-8元的杂芳环。
  4. 如权利要求1所述的化合物，其特征在于，所述的化合物选自下组：
    Figure PCTCN2021115459-appb-100006
    Figure PCTCN2021115459-appb-100007
  5. 如权利要求1所述的化合物的制备方法，其特征在于，包括步骤：
    Figure PCTCN2021115459-appb-100008
    (i)在惰性溶剂中，用式(II)化合物与RgH反应，得到式(I)化合物；
    或所述的方法包括步骤：
    Figure PCTCN2021115459-appb-100009
    (1)在惰性溶剂中，用式(III)化合物与CH 2＝CHCOOEt反应，得到式(IIIa)化合物；
    Figure PCTCN2021115459-appb-100010
    (2)在氢气气氛下，对式(IIIa)化合物进行还原，得到式(IIIb)化合物；
    Figure PCTCN2021115459-appb-100011
    (3)对式(IIIb)化合物进行水解脱保护，得到式(I-1)化合物；
    其中，M为F、Cl、Br或I。
  6. 如权利要求5所述的方法，其特征在于，所述的步骤(i)中，所述的方法在钯催化剂，配体和碱存在下进行；优选地，所述的钯催化剂为Pd 2(dba) 3，所述的碱为 tBuOK或Cs 2CO 3，且所述的配体选自下组：BrettPhos、RuPhos、XPhos或Pd 2(dba) 3；
    所述的步骤(1)中，所述的反应在钯催化剂，配体、碱和催化剂存在下进行；优选地，所述的钯催化剂为PdCl 2，所述的碱为碳酸钾，所述的配体为P(o-Tol) 3，且所述的催化剂为Bu 4NBr；
    所述的步骤(2)中，所述的反应在钯/碳存在下进行；
    所述的步骤(3)中，所述的反应在碱存在下进行；较佳地，所述的碱为NaOH。
  7. 如权利要求5所述的方法，其特征在于，所述的步骤(i)中，所述的惰性溶剂选自下组：叔丁醇、正丁醇、甲苯，或其组合；
    所述的步骤(1)中，所述的惰性溶剂选自下组：DMF、水，或其组合；
    所述的步骤(2)中，所述的惰性溶剂选自下组：乙酸乙酯；
    所述的步骤(2)中，所述的惰性溶剂选自下组：甲醇、水，或其组合。
  8. 一种液流电池储能材料，其特征在于，所述的液流电池储能材料是用如权利要求1-5任一所述的化合物作为活性成分制备的。
  9. 一种液流电池，其特征在于，所述的液流电池包括如权利要求1-5任一所述的化合物作为储能材料。
  10. 如权利要求9所述的液流电池，其特征在于，所述的液流电池中，如权利要求1-5任一所述的化合物作为负极或正极溶液。
PCT/CN2021/115459 2020-08-28 2021-08-30 基于吩嗪衍生物的电解质及其在液流电池中的应用 WO2022042735A1 (zh)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN202010892586 2020-08-28
CN202010892586.2 2020-08-28
CN202110185442.8A CN114105893A (zh) 2020-08-28 2021-02-10 基于氨基酸衍生物的电解质及其在液流电池中的应用
CN202110185442.8 2021-02-10

Publications (1)

Publication Number Publication Date
WO2022042735A1 true WO2022042735A1 (zh) 2022-03-03

Family

ID=80354703

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/115459 WO2022042735A1 (zh) 2020-08-28 2021-08-30 基于吩嗪衍生物的电解质及其在液流电池中的应用

Country Status (1)

Country Link
WO (1) WO2022042735A1 (zh)

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2604913A1 (de) * 1976-02-07 1977-08-11 Bayer Ag Verfahren zum faerben von synthetischen fasermaterialien
JPH01254957A (ja) * 1988-04-04 1989-10-11 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料の処理方法
JPH0695305A (ja) * 1991-10-25 1994-04-08 Konica Corp 光透過部と遮光部とを形成するハロゲン化銀写真感光材 料
JPH06258786A (ja) * 1993-03-09 1994-09-16 Konica Corp ハロゲン化銀写真感光材料の処理方法
CN103000924A (zh) * 2011-09-16 2013-03-27 清华大学 一种有机相双液流电池
CN105308785A (zh) * 2012-09-26 2016-02-03 哈佛大学校长及研究员协会 基于有机小分子的液流电池
CN106063017A (zh) * 2013-09-26 2016-10-26 哈佛大学校长及研究员协会 基于醌和氢醌的液流电池
US20180366757A1 (en) * 2017-06-16 2018-12-20 Battelle Memorial Institute Highly stable phenazine derivatives for aqueous redox flow batteries
US20190115594A1 (en) * 2017-10-17 2019-04-18 University Of Southern California Stable positive side material for all-organic flow battery
CN109687007A (zh) * 2018-11-26 2019-04-26 电子科技大学 一种有机醌类液流电池及其组建方法
WO2019157437A1 (en) * 2018-02-09 2019-08-15 President And Fellows Of Harvard College Quinones having high capacity retention for use as electrolytes in aqueous redox flow batteries
CN110212203A (zh) * 2019-05-22 2019-09-06 南京大学 一种碱性羟基吩嗪类有机液流电池及制备方法
CN110446771A (zh) * 2017-02-13 2019-11-12 Cmblu企划股份公司 氧化还原液流电池组电解质
WO2020035548A2 (en) * 2018-08-14 2020-02-20 Cmblu Projekt Ag Redox-active compounds and uses thereof

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2604913A1 (de) * 1976-02-07 1977-08-11 Bayer Ag Verfahren zum faerben von synthetischen fasermaterialien
JPH01254957A (ja) * 1988-04-04 1989-10-11 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料の処理方法
JPH0695305A (ja) * 1991-10-25 1994-04-08 Konica Corp 光透過部と遮光部とを形成するハロゲン化銀写真感光材 料
JPH06258786A (ja) * 1993-03-09 1994-09-16 Konica Corp ハロゲン化銀写真感光材料の処理方法
CN103000924A (zh) * 2011-09-16 2013-03-27 清华大学 一种有机相双液流电池
CN105308785A (zh) * 2012-09-26 2016-02-03 哈佛大学校长及研究员协会 基于有机小分子的液流电池
CN106063017A (zh) * 2013-09-26 2016-10-26 哈佛大学校长及研究员协会 基于醌和氢醌的液流电池
CN110446771A (zh) * 2017-02-13 2019-11-12 Cmblu企划股份公司 氧化还原液流电池组电解质
US20180366757A1 (en) * 2017-06-16 2018-12-20 Battelle Memorial Institute Highly stable phenazine derivatives for aqueous redox flow batteries
US20190115594A1 (en) * 2017-10-17 2019-04-18 University Of Southern California Stable positive side material for all-organic flow battery
WO2019157437A1 (en) * 2018-02-09 2019-08-15 President And Fellows Of Harvard College Quinones having high capacity retention for use as electrolytes in aqueous redox flow batteries
WO2020035548A2 (en) * 2018-08-14 2020-02-20 Cmblu Projekt Ag Redox-active compounds and uses thereof
CN109687007A (zh) * 2018-11-26 2019-04-26 电子科技大学 一种有机醌类液流电池及其组建方法
CN110212203A (zh) * 2019-05-22 2019-09-06 南京大学 一种碱性羟基吩嗪类有机液流电池及制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUJI KATAYAMA: "AStruCtureDeslgnOfNovelPhotobaseGenerator andApplicationofaPhotobaseGenerator toNegativePhotosensitivePolyimides", JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY, vol. 23, no. 4, 31 December 2010 (2010-12-31), pages 467 - 471, XP055903415 *

Similar Documents

Publication Publication Date Title
CN106977491B (zh) 螺[芴-9,9-氧杂蒽]类空穴传输材料及其应用
CN106188506B (zh) 一类含8-羟基喹啉衍生物合Cu(II)的聚合金属配合物染料敏化剂及其制备方法
CN105622442A (zh) 一种叔丁基螺二芴类化合物及其制备方法和应用
Liu et al. Tuning band structures of dyes for dye-sensitized solar cells: Effect of different π-bridges on the performance of cells
Deng et al. Branched chain polymeric metal complexes containing Co (II) or Ni (II) complexes with a donor–π–acceptor architecture: Synthesis, characterization, and photovoltaic applications
WO2022042735A1 (zh) 基于吩嗪衍生物的电解质及其在液流电池中的应用
CN110600612B (zh) 基于自组装工程的p-i-n型钙钛矿电池空穴传输层
CN110922392B (zh) 一种苯基为末端桥链的咔唑共敏剂及其制备方法
CN113999217B (zh) 一种新化合物、制备方法及其作为共敏剂的应用
CN103467712B (zh) 二维共轭萘并二呋喃基的半导体聚合物及其制备、用途
CN114105893A (zh) 基于氨基酸衍生物的电解质及其在液流电池中的应用
CN111171046B (zh) 一种基于四噻吩并吡咯的免掺杂空穴传输材料及其合成方法和应用
CN108795090B (zh) X型双锚固染料敏化剂及其制备方法和应用
CN111138451B (zh) 一种基于茚并[2,1-b]咔唑的免掺杂空穴传输材料及其制备方法和应用
JP5035502B2 (ja) キニザリン架橋金属錯体
CN109400622B (zh) 一种以氮吡咯噻吩为母核的不对称有机空穴传输材料及其合成方法和用途
CN109575005B (zh) 4,4’-二(烷基苯)联噻吩桥联硫脲三苯胺光敏染料及其制备方法
CN114249746A (zh) 一种螺芴氧杂蒽三芳胺类空穴传输材料及其制备方法和应用
CN114315856B (zh) 一种含吩嗪并二噻吩类免掺杂空穴传输材料及其制备方法和应用
CN115433090B (zh) 一种大黄酸类化合物、制备方法及其作为共敏剂的应用
CN114497662B (zh) 一种多电子六氮杂萘类化合物在水系液流电池中的应用
CN108947927A (zh) 一种侧链含高电子迁移率芳杂环的醇/水溶性有机小分子阴极界面材料
CN111171036B (zh) 一种吲哚[3,2-b]咔唑为核的空穴传输材料及其制备方法和应用
CN109836369A (zh) 一种螺茚类空穴传输小分子及其在钙钛矿太阳能电池的应用
Zhu et al. Novel dyes of branched chain polymeric metal complexes with benzodithiophene or hydroquinone derivatives as donor: synthesis, characterization, and photovoltaic performance for dye-sensitized solar cells

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21860567

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21860567

Country of ref document: EP

Kind code of ref document: A1