CN116036870A - Polyphenylene sulfide lithium extraction membrane and electrochemical activation method thereof - Google Patents
Polyphenylene sulfide lithium extraction membrane and electrochemical activation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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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
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Abstract
The invention relates to the fields of new energy sources, electrochemical lithium extraction and the like, and provides a pre-lithiated polyphenylene sulfide permeable membrane and an electrochemical activation method thereof, wherein the structure of the pre-lithiated polyphenylene sulfide permeable membrane is shown as a formula I;
after electrochemical pre-activation is carried out on the pre-lithiated polyphenylene sulfide permeable membrane, the structure is shown as a formula II;
the lithium ion penetration, the hydrophilicity and the ion selectivity of the activated pre-lithiated polyphenylene sulfide membrane are all obtainedGreatly improves the lithium ion battery and the salt lake lithium extraction, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of electrochemical lithium extraction, and particularly relates to a pre-lithiated polyphenylene sulfide permeable membrane with ion selectivity and an electrochemical activation method thereof.
Background
Lithium is considered an important strategic resource in this century, and to some extent, determines the development fate of the electric automobile industry. Therefore, lithium resource development and utilization are receiving great attention and importance in various countries.
Currently, more than 80% of available lithium resources on earth exist in salt lake brine, and the main salt lake lithium extraction methods at present are a precipitation method (CN 106629790A), a solvent extraction method (CN 106435219B) and an adsorption method (CN 114836621A), but the processes of the methods are complex and the cost is high. There are also methods for extracting lithium by electrochemical deintercalation (CN 102049238A), which cannot continuously extract lithium, and require manual electrode replacement, which is cumbersome to operate. The selective lithium extraction by ion exchange membrane electrodialysis has the advantages of simple operation and continuous production. Chinese patent No. CN113307334a discloses an ion sieve cathode for electrolytic cells containing polyphenylene sulfide, and an ion sieve using the cathode has good ion selectivity, and can realize selective enrichment of lithium ions. But unactivated polyphenylene sulfide is not hydrophilic and can limit ion enrichment efficiency. Currently, researchers have less studied on the membrane activation problem, mainly for the membrane used in the fuel cell field, and the commercial PBI membrane is activated by the acid leaching method in chinese patent No. CN 111682248A. The activation method has the advantages of complicated operation, long activation time and pollution caused by acid.
Disclosure of Invention
Aiming at the problems of low conductivity, poor wettability and low lithium extraction efficiency of the polyphenylene sulfide permeable membrane, the invention provides the polyphenylene sulfide lithium extraction membrane and the electrochemical activation method thereof, which enable the membrane to have ion selectivity and hydrophilicity, and the treatment method is simple and easy to control, has strong operability and is suitable for large-scale production.
The aim of the invention is achieved by the following technical scheme:
an electrochemical activation method of a polyphenylene sulfide lithium extraction membrane is characterized in that the electrochemical activation process is carried out in an electrodialysis device, and a pre-lithiated polyphenylene sulfide permeable membrane is placed in the electrodialysis device to separate a cathode chamber and an anode chamber; injecting a pre-extracted lithium solution into the anode chamber, and injecting a conductive solution into the cathode chamber; an anode plate (4) is arranged in the anode chamber, a cathode plate (5) is arranged in the cathode chamber, and the anode plate (4) and the anode plate (5) are activated by an external power supply to pre-lithiate the polyphenylene sulfide permeable membrane; the electrochemical activation process is carried out under the condition of constant voltage of 1-10V at 0-50 ℃, and when the current reaches the peak value, the pre-lithiated polyphenylene sulfide osmotic membrane is activated.
Further, the pre-extracted lithium solution comprises lithium-containing salt lake brine, waste lithium ion battery leaching liquid, seawater and mica lithium ore leaching liquid.
Further, the preparation process of the pre-lithiated polyphenylene sulfide permeable membrane comprises the following steps: uniformly mixing the pre-lithiated polyphenylene sulfide powder with Polytetrafluoroethylene (PTFE) in a low-temperature mixer below 0 ℃, mixing the dry powder by using a supersonic jet mill, wherein the air inlet pressure is 1-2MPa; adding an organic solvent into the mixed dry powder, and kneading the dry powder by an internal mixer to form a dough-like material; extruding and molding the dough-like material through a screw extruder to obtain a cake-like broadband with the thickness of 500-1000 mu m continuously; and then the continuous cake-shaped broadband is manufactured into the pre-lithiated polyphenylene sulfide film material with the thickness of 20-50 mu m by adopting a horizontal hot roller press with the temperature lower than 150 ℃, wherein the pressure of the horizontal roller is 2-10T.
Further, the mass ratio of the pre-lithiated polyphenylene sulfide powder to polytetrafluoroethylene is 100:2-5.
Further, the added organic solvent is any one or more of the following combinations: water, ethanol, ethylene glycol, propylene glycol, glycerol, isopropanol, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone; the solid content of the dough-like material is more than or equal to 50 percent.
Further, the pre-lithiated polyphenylene sulfide powder is prepared by the steps of:
mixing polyphenylene sulfide particles, a lithium ion complexing agent and a tetrachloro-p-benzoquinone anion complexing agent, placing the mixture in a reaction kettle which is continuously introduced with argon or nitrogen, heating to 200-400 ℃, reacting for 2-5h, then cooling to room temperature at a temperature of 1-2 ℃/min, washing the obtained product with deionized water for multiple times, filtering to neutrality, and vacuum drying at 60 ℃ for 12-24h to obtain the pre-lithiated polyphenylene sulfide powder.
Further, the mass ratio of the polyphenylene sulfide to the lithium ion complexing agent to the tetrachloro-p-benzoquinone is 100:5-15:15-50.
Further, the molecular structure of the pre-lithiated polyphenylene sulfide before electrochemical activation is as follows formula I:
the lithium ion complexing agent is Li + Is one or more of any combination of cations and X is an anion; the anion X is Cl - 、TFSI - 、FSI - 、F - 、BF 4 - Or PF (physical pattern) 6 - 。
The lithium extraction membrane of the polyphenylene sulfide prepared by the electrochemical activation method is characterized in that the molecular structure of the activated pre-lithiated polyphenylene sulfide is shown as a formula II:
the S-Li bond on the thioether bond in formula ii is broken and oxidized to s=o bond during the electro-activation process.
The invention to obtain a high Li + The aim of the pre-lithiated polyphenylene sulfide permeable membrane is ion selectivity, permeability and good hydrophilicity. Polyphenylene sulfide is used as raw material, and is pre-lithiatedThe semi-dry method is adopted to prepare a membrane, the surface of the membrane is subjected to oxidation reaction through a constant-current or constant-voltage electrochemical activation process, and S site on a polyphenylene sulfide chain on the surface of the membrane is oxidized into an S=O bond, so that the membrane is converted into a formula II from a formula I. The method is operated in situ in the electrodialysis lithium extraction process, is simple and direct, and is suitable for large-scale production and application.
High Li of the pre-lithiated polyphenylene sulfide permeable membrane at normal temperature is realized in an electrodialysis device through an electrochemical activation process of in-situ constant current or constant voltage + Ion permeation amount and good hydrophilicity. The ion permeation quantity of the polyphenylene sulfide ion permeable membrane after the activation treatment by the method is greatly improved, and the ion selectivity is obviously improved, which is hundreds of times of the ion permeation quantity of the common polyphenylene sulfide ion permeable membrane under the same experimental condition. The method is simple to operate, does not increase the manufacturing cost, has no additional requirement on a treatment link, obtains the diaphragm with high ion conduction and high ion selectivity, and has great application prospects in the fields of lithium ion batteries, salt lake lithium extraction and the like.
Drawings
FIG. 1 is a schematic diagram of an electrodialysis device used in an electrochemical activation process.
1 is a cathode chamber, 2 is an anode chamber, 3 is a permeable membrane, 4 is an anode plate, 5 is a cathode plate, 6 is an anode chamber wall, and 7 is a cathode chamber wall.
Detailed Description
For a clearer description of the technical solutions of the present invention, the following examples are given as illustrations of the specific experimental operation part of the present invention, which are only for illustrating the present invention, and are not to be construed as limiting the present invention.
In a specific implementation process, in the pre-lithiated polyphenylene sulfide permeable membrane with high ion conductivity and ion selectivity, the molecular structure of the pre-lithiated polyphenylene sulfide is as follows:
example 1
Firstly, uniformly mixing 100g of polyphenylene sulfide particles, 10g of lithium ion complexing agent LiTFSI and 30g of tetrachloro-p-benzoquinone anion complexing agent according to the mass ratio of 100:10:30, placing the mixture into a reaction kettle continuously introducing argon, heating to 200 ℃, reacting for 5 hours, cooling to room temperature according to the temperature control of 2 ℃ per minute, washing the obtained product with deionized water for multiple times, filtering to neutrality, and vacuum drying at 60 ℃ for 24 hours to obtain the pre-lithiated polyphenylene sulfide powder. Then, uniformly mixing 100g of pre-lithiated polyphenylene sulfide powder and 3g of Polytetrafluoroethylene (PTFE) in a low-temperature mixer at the temperature of minus 5 ℃ according to the mass ratio of 100:3, and then mixing in a supersonic jet mill with the air inlet pressure of 2MPa; adding a mixed solvent of water and ethanol into the mixed dry powder after PTFE wiredrawing, and kneading in an internal mixer to form a dough-like material with the solid content of 80%. Extruding the dough-like material into a pancake-like broadband with the continuous thickness of 500 mu m through a screw extruder; the continuous cake-shaped broadband was then subjected to a horizontal hot roll press at a temperature of 120℃to prepare a pre-lithiated polyphenylene sulfide film having a thickness of 30. Mu.m, under a pressure of 2T.
The electrodialysis device used for electrochemical activation according to the invention is shown in fig. 1, and a pre-lithiated polyphenylene sulfide permeable membrane 3 is placed in the electrodialysis device to separate an anode chamber 1 and a cathode chamber 2. The anode chamber 1 is surrounded by an anode chamber wall 6, into which a pre-extraction lithium solution is injected; the cathode chamber 2 is surrounded by a cathode chamber wall 7 into which an electrically conductive solution, for example a hydrochloric acid solution, is injected. An anode plate 4 is arranged in the anode chamber, a cathode plate 5 is arranged in the cathode chamber, and the cathode plate 4 and the anode plate 5 are connected with an external power supply.
The prepared pre-lithiated polyphenylene sulfide permeable membrane is put into an electrodialysis device to isolate a cathode chamber and an anode chamber, and the conductive cathode and the anode adopt platinum sheet electrodes, wherein the anode chamber is a mixed solution of magnesium chloride and lithium chloride, and the concentration of magnesium ions is 50 g.L -1 Lithium ion concentration of 1 g.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The cathode chamber was a 0.1M hydrochloric acid solution. After the power is turned on, the constant voltage activation current reaches a peak value under the voltage of 5V, and the electrochemical activation is completed. Then, the lithium extraction film was prepared by using the polyphenylene sulfide electrochemically activated in this example, and was subjected to constant current of 15 mA.cm -2 Electrodialysis is continued for 12h at the current density of Mg before and after activation 2+ /Li + The concentration ratio was changed from 50 to 49.3.
Examples 2 to 5
Examples 2-5 were prepared as the pre-lithiated polyphenylene sulfide permeable membrane of example 1, except that the conditions for electrochemical activation were different. The data after 12h lithium extraction of the same lithium extraction solution for the activated polyphenylene sulfide lithium extraction membranes under different constant pressure conditions are shown in table 1.
Example 6
Example 6 the same process as in example 1 for the preparation of the pre-lithiated polyphenylene sulfide permeable membrane, except that example 6 was directly subjected to electrodialysis experiments without activation.
TABLE 1 ion selectivity under different electrochemical activation conditions
Although embodiments of the present invention have been described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations may be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. An electrochemical activation method of a polyphenylene sulfide lithium extraction membrane is characterized in that the electrochemical activation process is carried out in an electrodialysis device, and a pre-lithiated polyphenylene sulfide permeable membrane is placed in the electrodialysis device to separate a cathode chamber and an anode chamber; injecting a pre-extracted lithium solution into the anode chamber, and injecting a conductive solution into the cathode chamber; an anode plate (4) is arranged in the anode chamber, a cathode plate (5) is arranged in the cathode chamber, and the anode plate (4) and the anode plate (5) are activated by an external power supply to pre-lithiate the polyphenylene sulfide permeable membrane; the electrochemical activation process is carried out under the condition of constant voltage of 1-10V at 0-50 ℃, and when the current reaches the peak value, the pre-lithiated polyphenylene sulfide osmotic membrane is activated.
2. The electrochemical activation method of the polyphenylene sulfide lithium extraction membrane according to claim 1, wherein the pre-extracted lithium solution comprises lithium-containing salt lake brine, waste lithium ion battery leaching solution, seawater and mica lithium ore leaching solution.
3. The electrochemical activation method of the polyphenylene sulfide lithium extraction membrane according to claim 1, wherein the preparation process of the pre-lithiated polyphenylene sulfide permeable membrane is as follows: uniformly mixing the pre-lithiated polyphenylene sulfide powder with Polytetrafluoroethylene (PTFE) in a low-temperature mixer below 0 ℃, mixing the dry powder by using a supersonic jet mill, wherein the air inlet pressure is 1-2MPa; adding an organic solvent into the mixed dry powder, and kneading the dry powder by an internal mixer to form a dough-like material; extruding and molding the dough-like material through a screw extruder to obtain a cake-like broadband with the thickness of 500-1000 mu m continuously; and then the continuous cake-shaped broadband is manufactured into the pre-lithiated polyphenylene sulfide film material with the thickness of 20-50 mu m by adopting a horizontal hot roller press with the temperature lower than 150 ℃, wherein the pressure of the horizontal roller is 2-10T.
4. The electrochemical activation method of the polyphenylene sulfide lithium extraction membrane according to claim 3, wherein the mass ratio of the pre-lithiated polyphenylene sulfide powder to polytetrafluoroethylene is 100:2-5.
5. The electrochemical activation method of the polyphenylene sulfide lithium extraction membrane according to claim 3, wherein the added organic solvent is any one or a combination of more of the following: water, ethanol, ethylene glycol, propylene glycol, glycerol, isopropanol, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone; the solid content of the dough-like material is more than or equal to 50 percent.
6. The electrochemical activation method of a lithium-extracted polyphenylene sulfide membrane according to claim 3, wherein the pre-lithiated polyphenylene sulfide powder is prepared by:
mixing polyphenylene sulfide particles, a lithium ion complexing agent and a tetrachloro-p-benzoquinone anion complexing agent, placing the mixture in a reaction kettle which is continuously introduced with argon or nitrogen, heating to 200-400 ℃, reacting for 2-5h, then cooling to room temperature at a temperature of 1-2 ℃/min, washing the obtained product with deionized water for multiple times, filtering to neutrality, and vacuum drying at 60 ℃ for 12-24h to obtain the pre-lithiated polyphenylene sulfide powder.
7. The electrochemical activation method of the polyphenylene sulfide lithium extraction membrane according to claim 5, wherein the mass ratio of the polyphenylene sulfide to the lithium ion complexing agent to the tetrachloro-p-benzoquinone is 100:5-15:15-50.
8. The electrochemical activation method of a lithium extraction membrane of polyphenylene sulfide according to claim 1, wherein the molecular structure of the pre-lithiated polyphenylene sulfide before electrochemical activation is as follows formula i:
the lithium ion complexing agent is Li + Is one or more of any combination of cations and X is an anion; the anion X is Cl - 、TFSI - 、FSI - 、F - 、BF 4 - Or PF (physical pattern) 6 - 。
9. The lithium extraction membrane of polyphenylene sulfide activated by the electrochemical activation method of claims 1-8, wherein the activated pre-lithiated polyphenylene sulfide has a molecular structure of formula ii:
the S-Li bond on the thioether bond in formula ii is broken and oxidized to s=o bond during the electro-activation process.
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