CN114195704A - Preparation method of TEMPO-quaternary ammonium salt for water-based flow battery - Google Patents
Preparation method of TEMPO-quaternary ammonium salt for water-based flow battery Download PDFInfo
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- CN114195704A CN114195704A CN202111504594.6A CN202111504594A CN114195704A CN 114195704 A CN114195704 A CN 114195704A CN 202111504594 A CN202111504594 A CN 202111504594A CN 114195704 A CN114195704 A CN 114195704A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
- C07D211/94—Oxygen atom, e.g. piperidine N-oxide
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- 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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
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- 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
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- 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
Abstract
The invention relates to the technical field of redox active materials of flow batteries, and particularly provides a preparation method of TEMPO-quaternary ammonium salt, which comprises the following steps: s1, adding 4-chloro-2, 2,6, 6-tetramethylpiperidine and tetramethylpropanediamine into a polar solvent for nucleophilic displacement reaction to obtain dichloronium salt; s2, under the action of a catalyst, performing oxidation reaction on the dichloride and peroxide in a solvent to obtain a target product TEMPO-quaternary ammonium salt; the invention mainly uses hydrogen peroxide to match with a magnesium hydroxide catalyst; hydrogen peroxide is matched with sodium tungstate; carrying out oxidation on tert-butyl hydroperoxide and cuprous chloride to obtain a target product; the method has the advantages that hydrogen peroxide is used as an oxidant, magnesium hydroxide catalyst and water are used as a solvent, the solvent is green and environment-friendly, the method accords with the concept of green production, the reaction and post-treatment processes are simple and easy to operate, the catalyst can be filtered and separated, recycled, the target product can be obtained through reduced pressure distillation, the raw material conversion rate is high, the method is environment-friendly, easy to amplify and suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of redox active materials of flow batteries, and particularly relates to a preparation method of TEMPO-quaternary ammonium salt for a water-based flow battery.
Background
The power generation of renewable clean energy sources such as wind energy, solar energy, water energy and tidal energy has the characteristics of volatility, intermittence, discontinuity and the like, influences the stability of a power supply system and is difficult to be directly utilized. The energy storage technology can realize the scheduling and control of the power balance of the renewable energy source and realize the high-efficiency conversion of energy.
The electrochemical energy storage technology has the advantages of high energy conversion efficiency, convenience in equipment installation, short construction period, low investment cost, convenience in maintenance and the like, and is widely researched and applied. The redox flow battery is a large-scale efficient electrochemical energy storage battery, particularly a water system flow battery, which adopts water-soluble characteristics as a solvent, has no potential risk of spontaneous combustion as long as no manufacturing error occurs during operation, is safe to use and is environment-friendly.
At present, the traditional flow battery is still based on inorganic redox substances, mainly focuses on single metal-based electroactive materials such as vanadium, chromium and iron, and has the defects of high rare cost of metal materials, strong corrosivity of electrolyte, slow kinetics, dendritic crystals and the like. Therefore, organic materials with good electrochemical properties are gradually applied to flow batteries, and energy is stored through redox reaction of organic active materials without participation of a catalyst. The organic active material can be artificially designed with a molecular structure, the electronic effect adjustment of organic functional groups is adopted, hydrophilic groups are added to improve the solubility, and the transmembrane effect can be reduced by adjusting the size of molecules or the charge density on the molecules. Therefore, the organic active molecular material is used for replacing metal ions as active substances of the positive electrode and the negative electrode of the flow battery, and is an important breakthrough for active substance development.
In a few positive electrode systems, TEMPO has high reversible 1 electron stable storage capacity and high oxidation-reduction potential, and shows great potential of application of positive electrode electroactive materials. However, due to the hydrophobic nature of the molecular backbone, TEMPO cannot be used in aqueous flow batteries. Aiming at the problem, the TEMPO-quaternary ammonium salt organic active material provided by the invention can be applied to a water system flow battery of a neutral system by improving the water solubility of the TEMPO-quaternary ammonium salt organic active material, does not cause adverse effects on equipment and pipelines, reduces the membrane permeability, reduces the cost of industrial production, and accords with the development strategy of sustainable green energy storage in the future.
In a report, patent CN109803955A discloses a method for synthesizing TEMPO-quaternary ammonium salt, which uses 4-aminoalkyl piperidyl compound and organic chloride as raw materials, and prepares TEMPO-quaternary ammonium salt by heating in aprotic organic solvent. Different from patent CN109803955A, the invention adopts 4-chloro-2, 2,6, 6-tetramethyl piperidine, 1, 3-dichloropropane and hydrogen peroxide to react in sequence, the reaction and post-treatment processes in the synthesis process are simple and easy to operate, and the catalyst can be filtered and separated for recycling, thereby conforming to the concept of green production.
Disclosure of Invention
In order to solve the problems, the invention discloses a preparation method of TEMPO-quaternary ammonium salt for a water-based flow battery.
In order to achieve the purpose, the technical scheme of the invention is as follows:
TEMPO-quaternary ammonium salt for an aqueous flow battery has a structural formula shown as a formula (I):
the molecular formula of the TEMPO-quaternary ammonium salt is C25H52Cl2N4O2。
Further, the method comprises the following steps:
s1: adding 4-chloro-2, 2,6, 6-tetramethylpiperidine and tetramethylpropanediamine into a polar solvent for nucleophilic displacement reaction to obtain dichloronium salt;
s2: under the action of a catalyst, carrying out oxidation reaction on a dichloride salt and peroxide in a solvent to obtain TEMPO-quaternary ammonium salt;
further, in step S1, the molar ratio of the 4-chloro-2, 2,6, 6-tetramethylpiperidine to the tetramethylpropanediamine is 1: 0.2 to 1; the total mass of the 4-chloro-2, 2,6, 6-tetramethylpiperidine and the tetramethylpropanediamine accounts for 10-90% of the total mass of the 4-chloro-2, 2,6, 6-tetramethylpiperidine, the tetramethylpropanediamine and the polar solvent.
Further, in step S1, the polar solvent is one or more of N, N-dimethylformamide, acetonitrile, dimethyl sulfoxide, methanol, and ethanol.
Further, in step S1, the temperature of the nucleophilic displacement reaction is 70-150 ℃, and the time of the nucleophilic displacement reaction is 8-24 h.
Further, in step S2, the mole ratio of the dichloride salt to the peroxide to the catalyst is 1: 3-12: 0.006-0.12; the total mass of the dichlorohydrin, the peroxide and the catalyst accounts for 20-80% of the total mass of the dichlorohydrin, the peroxide, the catalyst and the solvent.
Further, in step S2, the solvent is water.
Further, in step S2, the peroxide is hydrogen peroxide.
Further, in step S2, the catalyst is one or more of magnesium sulfate, magnesium hydroxide, sodium tungstate, copper chloride, and cuprous chloride.
Further, in step S2, the temperature of the oxidation reaction is 40-90 ℃, and the time of the oxidation reaction is 8-72 h.
The invention has the beneficial effects that:
1. the nucleophilic displacement reaction for preparing the target product uses water as a solvent, and the solvent is green and environment-friendly and accords with the concept of green production.
2. The whole process of the reaction and the post-treatment is simple and easy to operate, environment-friendly, easy to amplify and suitable for industrial production.
3. The preparation method has the advantages of high conversion rate of raw materials, high product purity, capability of filtering and separating the catalyst for recycling and high economic value.
Drawings
FIG. 1 is a HNMR map of a target product prepared in step S1 of example 1 of the present invention;
FIG. 2 is a HNMR map of the target product prepared in step S2 of example 1 of the present invention;
FIG. 3 is a simplified schematic of an electrochemical performance test;
fig. 4 is a graph of coulombic efficiency, voltage efficiency, energy efficiency and cycle number of the target product prepared in example 1 of the present invention.
Detailed Description
The present invention will be further illustrated with reference to the accompanying drawings and specific embodiments, which are to be understood as merely illustrative of the invention and not as limiting the scope of the invention.
Example 1
S1: 175g of 4-chloro-2, 2,6, 6-tetramethylpiperidine, 65g of tetramethylpropanediamine and 250g N, N-dimethylformamide are put into a four-neck round-bottom flask, the temperature is firstly increased to 80 ℃ in nitrogen atmosphere for reaction for 4 hours, then the temperature is increased to 150 ℃, the temperature is kept for reaction for 18 hours, and then the temperature is reduced to 40 ℃ for suction filtration, washing and drying to obtain 240g of white intermediate dichloride salt.
FIG. 1 shows a nuclear magnetic hydrogen spectrum diagram of structural formula I. 1H NMR (400MHz, D2O) δ = 3.76(m, 2H),3.24(s, 1H), 3.08(D, 16H), 2.18(t, 4H), 1.89(s, 1H), 1.73(t, 2H), 1.43(t, 2H), 1.22(m, 24H).
S2: dissolving 240g of dichloride and 2g of magnesium hydroxide in 250g of water, heating to 60 ℃, then dropwise adding 220g of 50wt.% hydrogen peroxide, keeping the temperature and reacting for 24 hours after dropwise adding, cooling, filtering, and distilling under reduced pressure to obtain 254g of orange TEMPO-quaternary ammonium salt (N1, N1, N3, N3-tetramethyl-N1, N3-bis (2,2,6, 6-tetramethyl piperidyloxy-4-yl) propane-1, 3-diaminochloride).
FIG. 2 shows a nuclear magnetic hydrogen spectrum diagram of formula II. 1H NMR (400MHz, D2O) δ = 3.89(m, 2H), 3.09(s, 16H), 2.95(s, 2H), 2.79(s, 2H), 2.29(D, 4H), 1.69(t, 4H),1.37(D, 24H).
Example 2
S1: 195.20g of 4-chloro-2, 2,6, 6-tetramethylpiperidine, 65.12g of tetramethylpropanediamine and 250g of acetonitrile are put into a four-neck round-bottom flask, the temperature is firstly raised to 85 ℃ in nitrogen atmosphere for reaction for 3.5h, then the temperature is raised to 142 ℃, the temperature is kept for reaction for 17h, and then the temperature is lowered to 40 ℃ for suction filtration, washing and drying to obtain 195.13g of white intermediate dichloride salt.
S2: 195.13g of dichlorohydrin, 2.35g of magnesium hydroxide and 220g of deionized water are added into a four-neck round-bottom flask, 165g of 50wt.% hydrogen peroxide is added dropwise at 40 ℃, the temperature rises during the dropwise addition, after the dropwise addition is finished, the temperature rises to 68 ℃, the reaction is kept for 30 hours, the temperature is reduced, the filtration is carried out, and the reduced pressure distillation is carried out, so that 197.27g of orange-colored TEMPO-quaternary ammonium salt is obtained.
Example 3
S1: 192g of 4-chloro-2, 2,6, 6-tetramethylpiperidine, 66g of tetramethylpropanediamine and 300g of acetonitrile are added into a four-neck round-bottom flask, nitrogen is replaced for three times, the temperature is firstly raised to 100 ℃, the reaction is carried out for 3 hours under the condition of heat preservation, then the temperature is raised to 130 ℃, the reaction is carried out for 19 hours under the condition of heat preservation, the temperature is lowered to 40 ℃, and the white intermediate dichloride salt of 189.34g is obtained after suction filtration, washing and drying.
S2: 189.34g of dichloride, 4.93g of sodium tungstate and 260g of deionized water are added into a four-neck round-bottom flask, 155g of 50wt.% hydrogen peroxide is dropwise added at 45 ℃, after dropwise addition is finished, the temperature is slowly raised to 60 ℃, heat preservation reaction is carried out for 30 hours, cooling and suction filtration are carried out, reduced pressure distillation is carried out, and 187.64g of orange TEMPO-quaternary ammonium salt is obtained.
Example 4
S1: 195.20g of 4-chloro-2, 2,6, 6-tetramethylpiperidine, 65.12g of tetramethylpropanediamine and 250g of dimethyl sulfoxide are put into a four-neck round-bottom flask, the temperature is firstly raised to 70 ℃ in nitrogen atmosphere for reaction for 5h, then the temperature is raised to 148 ℃ for reaction for 17h, the temperature is reduced to 40 ℃, and the white intermediate dichloride salt is obtained after suction filtration, washing and drying, wherein 169.32g of the white intermediate dichloride salt is obtained.
S2: 169.32g of dichloride salt, 3.2g of cuprous chloride and 280g of deionized water are put into a four-neck round-bottom flask, heated to 42 ℃, 136g of 70wt% hydrogen peroxide is added dropwise, after the dropwise addition is finished, the temperature is slowly raised to 65 ℃, the reaction is continued for 24 hours under heat preservation, the temperature is reduced, the filtration is carried out, and the distillation under reduced pressure is carried out, so that 169.32g of orange TEMPO-quaternary ammonium salt is obtained.
Example 5
S1: 195g of 4-chloro-2, 2,6, 6-tetramethylpiperidine, 65.2g of tetramethylpropanediamine and 250g of methanol are added into a four-neck round-bottom flask for three times of replacement by nitrogen, the temperature is firstly raised to 80 ℃ for reaction for 4h, then raised to 150 ℃, the temperature is reduced to 40 ℃ after the reaction is kept for 18h, and the white intermediate dichloride salt of 150.24g is obtained by suction filtration, washing and drying.
S2: 150.24g of dichlorohydrin, 4.5g of magnesium sulfate and 167g of deionized water are added into a four-neck round-bottom flask, 128g of 50wt.% hydrogen peroxide is dropwise added, the temperature rises in the dropwise adding process, after the dropwise adding is finished, the temperature is slowly raised to 60 ℃, the reaction is kept for 20 hours, the temperature is reduced, the filtration is carried out, and the reduced pressure distillation is carried out, so that 152.34g of orange TEMPO-quaternary ammonium salt is obtained.
Electrochemical performance test
The electrochemical performance testing instrument used in the patent is placed in an indoor environment, a battery performance test is carried out in a glove box filled with nitrogen, the battery consists of two liquid storage tanks, two current collecting plates, two graphite felt electrodes, two peristaltic pumps and an anion exchange membrane (the thickness is 8 mu m), and the schematic diagram of the battery is shown in attached figure 3. And after the assembly of the flow battery is completed, deoxidizing and purifying the electrolyte in the liquid storage tank by using high-purity nitrogen. In the experiment, a peristaltic pump is adopted to realize the circulation of the electrolyte, and the flow rate is 15 mL/min. The current density of the battery subjected to constant current charge and discharge test is 60 mA-cm-2The charge-discharge cut-off voltage is 0.2-1.2V. Wherein the battery test adopts 0.5mol/L of mono (1,1 '-bi (3- (trimethylamino) propyl) - [4,4' -bipyridyl]-1,1' -diimmonium) dichloride solution as a battery negative electrolyte, 0.5mol/L TEMPO-quaternary ammonium salt solution prepared in the embodiment 1 of the invention as a battery positive electrolyte, and NaCl solution supporting 1.2mol/L electrolyte are used for experiments, and deionized water is used as a solvent for battery tests. Fig. 4 shows the test results of the battery using the TEMPO-quaternary ammonium salt solution prepared in example 1 of the present invention as the battery positive electrolyte, after 100 cycles, the average coulombic efficiency was 99.17%, the average voltage efficiency was 91.94%, and the average energy efficiency was 88.69%, showing excellent cycle stability.
It should be noted that the above-mentioned contents only illustrate the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and it is obvious to those skilled in the art that several modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations fall within the protection scope of the claims of the present invention.
Claims (10)
1. TEMPO-quaternary ammonium salt for a water-based flow battery is characterized by having a structural formula shown as a formula (I):
the molecular formula of the TEMPO-quaternary ammonium salt is C25H52Cl2N4O2。
2. The preparation method of TEMPO-quaternary ammonium salt for the aqueous flow battery according to claim 1, which comprises the following steps:
s1: adding 4-chloro-2, 2,6, 6-tetramethylpiperidine and tetramethylpropanediamine into a polar solvent for nucleophilic displacement reaction to obtain dichloronium salt;
s2: under the action of a catalyst, carrying out oxidation reaction on a dichloride salt and peroxide in a solvent to obtain TEMPO-quaternary ammonium salt;
3. the method for preparing TEMPO-quaternary ammonium salt for an aqueous flow battery according to claim 2, wherein the molar ratio of 4-chloro-2, 2,6, 6-tetramethylpiperidine to tetramethylpropanediamine in step S1 is 1: 0.2 to 1; the total mass of the 4-chloro-2, 2,6, 6-tetramethylpiperidine and the tetramethylpropanediamine accounts for 10-90% of the total mass of the 4-chloro-2, 2,6, 6-tetramethylpiperidine, the tetramethylpropanediamine and the polar solvent.
4. The method for preparing TEMPO-quaternary ammonium salt for an aqueous flow battery according to claim 2, wherein in step S1, the polar solvent is one or more of N, N-dimethylformamide, acetonitrile, dimethyl sulfoxide, methanol and ethanol.
5. The method for preparing TEMPO-quaternary ammonium salt for an aqueous flow battery according to claim 2, wherein the temperature of nucleophilic substitution reaction is 70-150 ℃ and the time of nucleophilic substitution reaction is 8-24h in step S1.
6. The method for preparing TEMPO-quaternary ammonium salt for water-based flow batteries according to claim 2, wherein the mole ratio of the dichloride salt to the peroxide to the catalyst in step S2 is 1: 3-12: 0.006-0.12; the total mass of the dichlorohydrin, the peroxide and the catalyst accounts for 20-80% of the total mass of the dichlorohydrin, the peroxide, the catalyst and the solvent.
7. The method for preparing TEMPO-quaternary ammonium salt for water-based flow batteries according to claim 2, wherein in step S2, the solvent is water.
8. The method for preparing TEMPO-quaternary ammonium salt for the water-based flow battery according to claim 2, wherein in step S2, the peroxide is hydrogen peroxide.
9. The method for preparing TEMPO-quaternary ammonium salt for the water-based flow battery according to claim 2, wherein in step S2, the catalyst is one or more of magnesium sulfate, magnesium hydroxide, sodium tungstate, copper chloride and cuprous chloride.
10. The method for preparing TEMPO-quaternary ammonium salt for water-based flow batteries according to claim 2, wherein the temperature of the oxidation reaction is 40-90 ℃ and the time of the oxidation reaction is 8-72h in step S2.
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2021
- 2021-12-10 CN CN202111504594.6A patent/CN114195704A/en active Pending
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