CN113563581B - Teller lattice base polymer ion exchange membrane material containing zwitter-ion structure of negative and positive ions and preparation method and application thereof - Google Patents
Teller lattice base polymer ion exchange membrane material containing zwitter-ion structure of negative and positive ions and preparation method and application thereof Download PDFInfo
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- CN113563581B CN113563581B CN202110844967.8A CN202110844967A CN113563581B CN 113563581 B CN113563581 B CN 113563581B CN 202110844967 A CN202110844967 A CN 202110844967A CN 113563581 B CN113563581 B CN 113563581B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0694—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring, e.g. polyquinoxalines
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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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
- 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
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a Teller's base polymer ion exchange membrane material containing a zwitter-ion structure and a preparation method and application thereof. The structural formula of the material is shown as follows, X is C substituted by anion1～C4An alkyl group, the anion being a sulfonate anion [ -S (═ O) -O‑]Or carboxylate anion [ -C (═ O) -O‑]And n is 200-1200. The method is characterized in that positive and negative zwitterions are introduced into a rigid main chain of the obtained Teller alkali polymer membrane material by a simple one-pot method. The polymer amphoteric ion exchange membrane material obtained by the invention contains positive and negative amphoteric ions at the same time. The introduction of quaternary ammonium cations can effectively adsorb negatively charged polysulfide generated in the discharge process of the lithium-sulfur battery; the introduction of negatively charged sulfonic acid groups or acetate groups can increase the transmission of lithium ions, and the lithium sulfur battery has good application value.
Description
Technical Field
The invention belongs to the field of polymer amphoteric ion exchange membranes, and particularly relates to preparation and application of a polymer ion exchange membrane material containing a anion-cation amphoteric ion structure and a Teller base.
Background
With the sharp increase of modern energy demand and the improvement of environmental protection consciousness, research and development of a novel high-efficiency clean new energy for replacing the traditional fossil energy has important academic and practical application values. The lithium-sulfur battery is a device for directly converting chemical energy into electric energy through electrochemical reaction, and has ultrahigh theoretical specific capacity (1675mAh g)-1) And theoretical energy density (2567Wh kg)-1) And the lithium ion battery is far higher than the traditional lithium ion battery, and is expected to become a next-generation novel rechargeable battery. The diaphragm plays a very important role in the battery, and not only can separate the positive electrode and the negative electrode of the battery to prevent short circuit, but also can promote the transmission of lithium ions. However, although the pore size of the conventional commercial separator has been made smaller in recent years, it has not been able to completely block polysulfides generated during discharge, causing a shuttle effect, which affects the performance of the battery. Membrane finishing may solve this problem well. Most of the modified layers currently do not combine the shuttle effect suppression and the lithium ion transport promotion.Therefore, the development of a diaphragm modification layer material which can inhibit the shuttle effect and promote the lithium ion transmission is of great significance and becomes a hot spot of the current research.
The study of the polymer membrane materials of Teller Geine, the backbone of which comprises twisted polymer chains of V-shaped rigid Teller Geine basic units, with inefficient packing providing inherent microporosity, has advanced considerably in recent years. However, the currently reported charged membrane materials of the Teller's base polymer are very few, and particularly, the material which can form a membrane by carrying positive and negative charges on a rigid main chain is also available.
Disclosure of Invention
The invention aims to provide a preparation method and application of a Teller basic group polymer ion exchange membrane material containing a zwitter-ion structure of anions and cations aiming at the defects in the prior art. The method adopts a simple one-pot method to obtain the Teller Gealkali polymer membrane material, and positive and negative zwitterions are introduced to a rigid main chain. The polymer amphoteric ion exchange membrane material obtained by the invention contains positive and negative amphoteric ions at the same time. The introduction of quaternary ammonium cations can effectively adsorb negatively charged polysulfide generated in the discharge process of the lithium-sulfur battery; the introduction of negatively charged sulfonic acid groups or carboxyl groups can increase the transmission of lithium ions, provide a new idea and method for the design, preparation and modification of the amphoteric ion exchange membrane material, and the related amphoteric ion exchange membrane material has good application value in the lithium-sulfur battery.
The technical scheme of the invention is as follows:
a Teller basis polymer ion exchange membrane material containing a zwitter-ion structure of anions and cations is disclosed, wherein the structural formula of the material is as follows:
wherein the structural unit contains quaternary ammonium cation and anion containing X, and the molar ratio of the quaternary ammonium cation to the anion containing X is 1: 1; n represents a polymerization degree and is a positive integer, and n is 50 to 2000.
X is C substituted by anions1～C4Alkyl, the anion being sulfoAcid radical anion [ -S (═ O) (-O) -O-]Or carboxylate anion [ -C (═ O) -O-]。
The preparation method of the Teller's basic group polymer ion exchange membrane material containing the zwitter-ion structure comprises the following steps:
(1) adding o-tolidine and dimethoxymethane into a first reactor under the protection of nitrogen and ice water bath, stirring, adding a catalyst, stirring and reacting for 24-120 h at 0-50 ℃, pouring the product into dilute ammonia water for settling, washing with deionized water until the solution is neutral, performing vacuum drying to obtain a crude product, and purifying to obtain a Teller-Gebase polymer;
wherein the mass ratio is ortho-tolidine: dimethoxymethane is 1: 2-8; the catalyst is trifluoroacetic acid, and the mass of the trifluoroacetic acid is 12-25 times that of the o-tolidine;
the concentration of the dilute ammonia water is 5-20%;
(2) respectively adding the Teller Gemachine base polymer and the organic solvent into a second reactor, stirring at room temperature until the solid is completely dissolved, adding an anion donor, stirring at 0-180 ℃ for 12-96 hours, pouring the reactant into ethyl acetate for settling, and washing and drying the solid to obtain the Teller Gemachine base polymer ion exchange membrane material containing the zwitter-ion structure;
wherein the anion donor is 1, 3-propane sultone or bromoacetic acid; the molar ratio is the polymer of Teller Gealkali: an anion donor is 1: 0.1-3; the mass of the organic solvent is 10-80 times of that of the Teller-G base polymer;
the organic solvent in the step (2) is N-methylpyrrolidone, N-dimethylformamide or dimethyl sulfoxide;
the purification of the Teller base polymer comprises the following steps: and (3) repeating the step of dissolving the solid in the organic solvent and then pouring the solid into methanol to separate out the solid for 2-5 times to obtain the purified Teller-Gebase polymer.
The solvent in the purification is dichloromethane or trichloromethane.
The application of the polymer ion exchange membrane material containing the anion-cation zwitter ion structure Teller base is used for modifying a battery diaphragm to enhance the performance of a lithium-sulfur battery.
The invention has the substantive characteristics that:
due to structural stability and limitation on a synthetic strategy, the currently reported Teller base polymer membrane materials are basically V-shaped structures containing rigid main chains and are electrically neutral.
The invention relates to a preparation method for introducing positive and negative zwitterions into a Teller-Gealkali polymer membrane material on a rigid main chain by adding a 1, 3-propane sultone or bromoacetic acid raw material, wherein the polymer zwitterion exchange membrane material simultaneously contains the positive and negative zwitterions. The introduction of quaternary ammonium cations can effectively adsorb negatively charged polysulfides generated in the discharging process of the lithium-sulfur battery; the introduction of negatively charged X groups can increase the transport of lithium ions.
The invention has the beneficial effects that:
(1) the invention provides a preparation method and application of a Telegrian base polymer ion exchange membrane material containing an anion-cation zwitterion structure, the synthesis and preparation route of the membrane material is simple and convenient, and the ion content can be effectively regulated and controlled through the dosage of 1, 3-propane sultone or bromoacetic acid;
(2) the ion exchange membrane material of the polymer with the anion-cation zwitter ion structure and the Teleger base has good membrane forming property, can be dissolved in solvents such as N-methylpyrrolidone, N-dimethylformamide or dimethyl sulfoxide and the like, and can be conveniently coated on a battery diaphragm by utilizing the solution to modify the diaphragm; as shown in fig. 3, the unmodified separator assembled battery specific capacity was from the initial 1200mAh g-1Attenuation to 751mAh g-1(ii) a The specific capacity of the battery assembled by the diaphragm modified by the Teller-Ge base polymer is from 1200mAh g-1Decays to 970mAh g-1(ii) a The specific capacity of the battery assembled by the diaphragm after being modified by the ion exchange membrane material containing the anion-cation zwitterion structure Teller-Gease polymer is from 1200mAh g-1Decay to 1027mAh g-1It can be seen that the modified ion exchange membrane material containing the anion-cation zwitterion structure Teller base polymer has good membrane circulation performance and is suitable for polysulfideThe blocking effect of (2) is the best.
(3) Quaternary ammonium cations in the Tiger base polymer ion exchange membrane material containing the zwitter-ion structure can effectively adsorb polysulfide with negative electricity generated in the discharging process of the lithium-sulfur battery; the introduction of the negatively charged X group can increase the transmission of lithium ions, and the membrane material has potential application value in lithium-sulfur batteries.
Drawings
FIG. 1 is a Fourier infrared spectrum of a Teller base polymer in example 1.
FIG. 2 is a Fourier infrared spectrum of a Legionene base polymer ion exchange membrane material with a sulfonic acid group anion-cation zwitterion structure;
FIG. 3 is a graph of measured cycle performance of an unmodified battery diaphragm, a battery assembled from a diaphragm modified with a Teller base polymer and an ion exchange membrane material comprising a sulfonate anion and cation zwitterion structure Teller base polymer;
FIG. 4 is a Fourier infrared spectrum of a Teller base polymer ion exchange membrane material containing a carboxylic acid group anion-cation zwitterion structure;
Detailed Description
Example 1
The specific synthetic route of the telange base polymer ion exchange membrane material containing the zwitter-ion structure of the anion and cation of the embodiment is as follows:
(1) respectively adding 5g (23.5mmol) of o-tolidine and 25ml of dimethoxymethane into a 250ml dry three-neck flask with mechanical stirring, nitrogen protection and ice-water bath, stirring until the o-tolidine and the dimethoxymethane are uniformly dispersed, then dropwise adding 60ml of trifluoroacetic acid through a constant pressure funnel, naturally recovering the room temperature, reacting for 72 hours, pouring the product into 90ml of dilute ammonia water with the mass concentration of 8%, then washing for 3 times by using a large amount of deionized water until the solution is neutral to obtain a fibrous Teller-Gebase polymer crude product with the yield of 99%, and then adding the product into dichloromethaneDissolving completely, and pouring into methanol to obtain precipitate; repeating twice the steps of adding dichloromethane for dissolution and pouring methanol for precipitation to obtain the purified Teller base polymer; FT-IR is shown in FIG. 1. At 1670cm-1The absorption band appeared to represent the C-N peak in the Teller base, indicating successful synthesis of the Teller base polymer. The polymerization degree n of the obtained Teller gilg base polymer is 200-1200;
in a 100ml dry single-neck flask with mechanical stirring, 0.4962g (2mmol) of Teller's base polymer is dissolved in 25ml of N-methylpyrrolidone solvent, 0.1466g (1.2mmol) of 1, 3-propanesulfonic lactone is added, the reaction is ended after 48 hours of reaction at 120 ℃, the reaction solution is poured into ethyl acetate for sedimentation, filtered and further washed for 3 times by using a large amount of ethyl acetate, and the ion exchange membrane material containing the Teller's base polymer with the zwitter-ion structure can be obtained after drying, wherein the yield is 98%; FT-IR is shown in FIG. 2. Similarly, at 1670cm-1The absorption band which appears represents the C-N peak in Teller-Gum base and is at 1032cm-1And 1235cm-1The absorption band at the position represents an S ═ O peak, which indicates that the synthesis of the Tilleger base polymer ion exchange membrane material containing the zwitterion structure is successful.
And (3) performance characterization test:
(1) adding 1.4mg of Teller's basic polymer and a Teller's basic polymer ion exchange membrane material with a sulfonic acid group-containing anion-cation zwitter-ion structure into 2 20ml glass bottles, adding 278.6mg of N-methylpyrrolidone to prepare a solution with the mass fraction of 0.5%, performing ultrasonic treatment for 1 hour until the solid is completely dissolved, and filtering through a polytetrafluoroethylene filter membrane to obtain a pure solution.
(2) And (3) placing the diaphragm on a spin-coating instrument, respectively dropwise adding 280mg of solution, spin-coating for one minute at the rotating speed of 500 revolutions per minute, and then placing the diaphragm in a 60 ℃ oven for drying for 12 hours to obtain the battery diaphragm modified by the Teleger base polymer and the Teleger base polymer ion exchange membrane material with the sulfonic group-containing anion-cation amphoteric ion structure.
(3) Adding the multi-wall carbon nano tube and the sublimed sulfur into an agate mortar according to the mass ratio of 1:3, grinding for 30 minutes, putting the ground solid into a hydrothermal kettle, and heating for 12 hours at 155 ℃. After the reaction was completed and the temperature was returned to room temperature, the solid was taken out, and the reaction was carried out as follows: conductive carbon black: grinding polyvinylidene fluoride in an agate mortar at a ratio of 7:2:1 for 30 minutes, dropwise adding a proper amount of N-methylpyrrolidone to prepare slurry, uniformly scraping the slurry on an aluminum foil by a scraper of 15 micrometers, drying in an oven at 60 ℃ for 6 hours, and cutting into a positive plate with the diameter of 1 cm.
(4) In a glove box with the water oxygen content lower than 0.01ppm, a CR2032 type battery is assembled from bottom to top according to the sequence of a positive electrode shell, a positive electrode plate, electrolyte, a diaphragm, a lithium plate, a gasket, an elastic sheet and a negative electrode shell, and the cycle performance of the battery is measured on a battery test station.
Fig. 3 is a graph showing the cycle performance of a lithium sulfur battery equipped with three different separators, and it can be seen from the graph that the three batteries have the same initial capacity because the initial capacity of the battery is related to the cathode material and the same material has the same initial capacity. The three batteries have the same initial specific capacity, but the battery specific capacity assembled by the unmodified separator is from the initial 1200mAh g-1Attenuation to 751mAh g-1(ii) a The specific capacity of the battery assembled by the diaphragm modified by the Teller-Ge base polymer is from 1200mAh g-1Decays to 970mAh g-1(ii) a The specific capacity of the battery assembled by the diaphragm after being modified by the ion exchange membrane material containing the anion-cation zwitterion structure Teller-Gease polymer is from 1200mAh g-1Attenuation to 1027mAh g-1It can be seen that the modified ion exchange membrane material containing the cationic and anionic zwitterionic Teller base polymer has the best cycle performance and the best barrier effect on polysulfide.
Table 1 shows the migration number of lithium ions measured after the battery is assembled by the unmodified battery separator, the polymer with theleneger bases and the ion exchange membrane material of the polymer with theleneger bases and containing zwitter-anions and zwitter-ions.
TABLE 1
As can be seen from the data in table 1, the transfer number of lithium ions of the separator modified with the telanger base polymer was reduced compared to the unmodified separator because: (1) the thickness of the diaphragm modified by the Teller-G base polymer is increased; (2) the telanger base polymer is electrically neutral and does not have the effect of increasing lithium ion transport. Although the thickness of the diaphragm modified by the anion-cation amphoteric ion structure containing sulfonic acid group and the Teller base polymer ion exchange membrane material is increased compared with that of the unmodified diaphragm, the abundant sulfonic acid groups on the structure can increase lithium ion transmission, so that the transference number of the lithium ions is higher than that of the unmodified diaphragm. The membrane material has potential application value in lithium-sulfur batteries.
Example 2
The other steps are the same as example 1 except that the starting material, 1, 3-propanesultone, is replaced with bromoacetic acid. To obtain the anion-cation exchange membrane material containing carboxylic groups. The infrared spectrum is shown in figure 4, and compared with Teller's base polymer, the anion-cation exchange membrane material containing carboxylic acid group is 2500cm-1An obvious absorption peak exists, which indicates that the carboxylic acid group is successfully introduced into the Teller-Kwangsi base polymer and the carboxylic acid group-containing anion-cation exchange membrane material is successfully synthesized.
The invention is not the best known technology.
Claims (7)
1. A Teller basis polymer ion exchange membrane material containing a zwitter-ion structure of anions and cations is characterized in that the structural formula of the material is as follows:
wherein the structural unit contains quaternary ammonium cation and anion containing X, n represents polymerization degree and is a positive integer, and n is 50-2000;
x is C substituted by anions1～C4Alkyl, the anion being a sulfonate anion [ -S (═ O) -O [ -S (═ O) ]-]Or carboxylate anion [ -C (═ O) -O-]。
2. The method for preparing the Teller basis polymer ion exchange membrane material containing the zwitter-ionic structure according to claim 1, wherein the method comprises the following steps:
(1) adding o-tolidine and dimethoxymethane into a first reactor under the protection of nitrogen and ice water bath, stirring, adding a catalyst, stirring and reacting for 24-120 h at 0-50 ℃, pouring the product into dilute ammonia water for settling, washing with deionized water until the solution is neutral, performing vacuum drying to obtain a crude product, and purifying to obtain a Teller-Gebase polymer;
wherein the mass ratio is that o-tolidine: dimethoxymethane is 1: 2-8; the catalyst is trifluoroacetic acid, and the mass of the trifluoroacetic acid is 12-25 times that of the o-tolidine;
(2) respectively adding the Teller Gemachine base polymer and the organic solvent into a second reactor, stirring at room temperature until the solid is completely dissolved, adding an anion donor, stirring at 0-180 ℃ for 12-96 hours, pouring the reactant into ethyl acetate for settling, and washing and drying the solid to obtain the Teller Gemachine base polymer ion exchange membrane material containing the zwitter-ion structure;
wherein the anion donor is 1, 3-propane sultone or bromoacetic acid; the molar ratio is the polymer of Teller Gealkali: an anion donor is 1: 0.1-3; the mass of the organic solvent is 10-80 times of that of the Teller-G base polymer.
3. The method for preparing the Teller base polymer ion exchange membrane material containing the zwitter-ionic structure according to claim 2, wherein the organic solvent in the step (2) is N-methylpyrrolidone, N-dimethylformamide or dimethyl sulfoxide.
4. The method for preparing the Teller basis polymer ion exchange membrane material containing the zwitter-ionic structure according to claim 2, wherein the purification of the Teller basis polymer comprises the following steps: and (3) repeating the step of dissolving the solid in the organic solvent and then pouring the solid into methanol to separate out the solid for 2-5 times to obtain the purified Teller-Gebase polymer.
5. The method for preparing the Teller basis polymer ion exchange membrane material containing the zwitter-ionic structure according to claim 2, wherein the concentration of the dilute ammonia water is 5-20%.
6. The method for preparing the Telleger base polymer ion exchange membrane material containing zwitter-ionic structures according to claim 2, wherein the solvent used in purification is dichloromethane or trichloromethane.
7. The use of the polymeric anion exchange membrane material comprising zwitterions of the structure of zwitterions of thetlergooth claim 1 as a battery separator.
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