CN115624958B - Film for extracting lithium from salt lake brine, preparation method thereof and lithium extraction method - Google Patents

Film for extracting lithium from salt lake brine, preparation method thereof and lithium extraction method Download PDF

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CN115624958B
CN115624958B CN202211164706.2A CN202211164706A CN115624958B CN 115624958 B CN115624958 B CN 115624958B CN 202211164706 A CN202211164706 A CN 202211164706A CN 115624958 B CN115624958 B CN 115624958B
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lithium
film
salt lake
lake brine
slurry
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CN115624958A (en
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刘亭
李有杰
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Foshan Southern China Institute For New Materials
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0211—Compounds of Ti, Zr, Hf
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3441—Regeneration or reactivation by electric current, ultrasound or irradiation, e.g. electromagnetic radiation such as X-rays, UV, light, microwaves
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • 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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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention discloses a film for extracting lithium from salt lake brine, a preparation method thereof and a lithium extraction method, and relates to the technical field of electrode materials. The preparation method of the film comprises the following steps: (1) Mixing an inorganic ion sieve adsorbent, a conductive additive organic binder and an organic solvent to obtain slurry; wherein the content of the organic solvent in the slurry is 40-60 wt%, and the weight ratio of the inorganic ion sieve adsorbent, the conductive additive and the organic binder is (80-98): (1-5): (1-20); (2) Forming a coating on the surface of the current collector by adopting the slurry, and curing to obtain a finished product; wherein, the current collector is selected from metal foil, semiconductor foil and conductive nonmetallic film. By implementing the invention, the adsorption capacity and the adsorption rate of the film can be improved, and the lithium extraction amount and the lithium extraction efficiency can be improved.

Description

Film for extracting lithium from salt lake brine, preparation method thereof and lithium extraction method
Technical Field
The invention relates to the technical field of electrode materials, in particular to a film for extracting lithium from salt lake brine, a preparation method thereof and a lithium extraction method.
Background
The salt lake brine is dominant in the world lithium salt production process, and reaches about 80% of the total yield, but the proportion of the total yield of the lithium salt is lower by adopting the salt lake brine to extract the lithium in China. The main reason is that the salt lake brine in China has higher magnesium and lithium ratio and high lithium extraction difficulty. Aiming at brine with high magnesium-lithium ratio and low lithium concentration, the adsorption method has great advantages in economy and environmental protection, and the method has the advantages of relatively simple process, lower energy consumption, high recovery rate and good selectivity, and is a preferable process scheme. The adsorbents (ion sieves) used in the adsorption method are generally classified into organic adsorbents and inorganic adsorbents.
Organic adsorbents are mainly used for researching crown ether, and the cost is high and the application is limited at present. The inorganic adsorbent is mainly divided into manganese-containing adsorbent, titanium-containing adsorbent, aluminum-containing adsorbent, antimonate lithium adsorbent and the like, and has higher selectivity. The principle is as follows: the composite lithium-containing metal oxide is formed by calcination, and then lithium of the oxide is replaced with hydrogen by an ion exchange reaction soaked in a strong acid. The oxide after acid leaching can extract lithium in low brine concentration through ion exchange reaction again. And (3) carrying out acid leaching again on the ion sieve after extracting lithium to realize desorption of lithium ions. The inorganic adsorbent has high selectivity and is very suitable for extracting lithium ions from brine with high magnesium-lithium ratio. However, inorganic ion sieve powder has the problems of smaller granularity and poorer fluidity, and contradiction such as powder deficiency, difficult recycling and the like can occur in industrial application. In order to solve such problems, there are common improvements such as granulating the powder and then adsorbing the powder, or preparing the powder into a slurry and then hanging the slurry on a mesh membrane. However, in these improvements, a large amount of auxiliary agents such as an organic binder and a surfactant are required to be added, and the adsorption capacity and the ion exchange rate are reduced, so that the operation period is greatly increased, the continuous production is not possible, and huge equipment is required to be used.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the preparation method of the film for extracting lithium from the salt lake brine, and the prepared film has higher adsorption capacity and adsorption rate, so that the lithium extraction efficiency can be effectively improved.
The invention also solves the technical problem of providing the film for extracting lithium from salt lake brine, which has higher adsorption capacity and adsorption rate and can effectively improve the lithium extraction efficiency.
The invention also solves the technical problem of providing a method for extracting lithium from salt lake brine, which has high lithium extraction efficiency.
In order to solve the problems, the invention discloses a preparation method of a film for extracting lithium from salt lake brine, which comprises the following steps:
(1) Mixing an inorganic ion sieve adsorbent, a conductive additive organic binder and an organic solvent to obtain slurry; wherein the content of the organic solvent in the slurry is 40-60 wt%, and the weight ratio of the inorganic ion sieve adsorbent, the conductive additive and the organic binder is (80-98): (1-5): (1-20);
(2) Forming a coating on the surface of the current collector by adopting the slurry, and curing to obtain a finished product;
wherein, the current collector is selected from metal foil, semiconductor foil and conductive nonmetallic film.
As an improvement of the technical scheme, the inorganic ion sieve adsorbent is one or more of titanium ion sieve adsorbent, manganese ion sieve adsorbent, chromium-containing lithium ion sieve adsorbent, aluminum-based lithium adsorbent and antimonate lithium adsorbent;
The organic binder is one or more of PVDF, PEO, PTFE, PAN, PI, PAA, PVA, sodium alginate, styrene-butadiene rubber and SBS, SEBS, NBR, HNBR;
The conductive additive is one or more of SuperP, carbon black and carbon nano tubes;
The organic solvent is selected from one or more of NMP, DMF, toluene, xylene, n-heptane, cyclohexane, ethanol and isopropanol.
As an improvement of the technical scheme, the inorganic ion sieve adsorbent is a titanium ion sieve;
the organic binder is PVDF and/or PVA;
the organic solvent is NMP and/or xylene.
As an improvement of the technical scheme, in the step (2), the slurry is scraped on the surface of a current collector, and a coating with the thickness of 50-120 mu m is formed on the surface of the current collector, and the finished product is obtained after heating and curing.
Correspondingly, the invention also discloses a film for extracting lithium from salt lake brine, which is prepared by the preparation method.
Correspondingly, the invention also discloses a method for extracting lithium from salt lake brine, which comprises the following steps:
(1) Placing the film into brine, and adsorbing for a preset time;
(2) And removing lithium ions in the absorbed film to obtain the lithium ion battery.
As an improvement of the above technical solution, the step (2) includes:
(2.1) placing the absorbed film into an electrolytic cell, and carrying out electrolytic reaction by taking the absorbed film as a cathode;
(2.2) transferring the film after the electrolytic reaction to an anode of an electrolytic cell, and taking another new film after the adsorption as a cathode to perform the electrolytic reaction; after the electrolytic reaction is finished, the film of the anode is used for removing lithium ions and absorbing brine as a new film; obtaining a lithium ion-rich solution in an electrolytic cell where an anode is positioned;
the electrolytic cell comprises a power supply, an electrolytic cell, an ion permeable membrane and an electrode socket, wherein the ion permeable membrane is arranged in the electrolytic cell, and the electrode socket is used for inserting the membrane, and hydrogen ions can permeate through the ion permeable membrane.
As an improvement of the technical scheme, an acidic electrolyte or a solvent is arranged in the electrolytic tank;
the acidic electrolyte is one or more of sulfuric acid, hydrochloric acid, hexafluorophosphoric acid and lithium bis (trifluoromethanesulfonyl) imide;
The solvent is one or more of EC, DMC, DEC, EMC, PC and water.
As an improvement of the technical scheme, in the step (1), the film is immersed in brine for 6-48 hours, taken out, washed and dried.
As an improvement of the technical scheme, in the step (2.1), when the electrolytic cell performs the primary reaction, the positive electrode material of the lithium ion battery is used as the anode.
The implementation of the invention has the following beneficial effects:
1. According to the preparation method of the film for extracting lithium from salt lake brine, firstly, an inorganic ion sieve adsorbent, a conductive additive, an organic binder and an organic solvent are mixed into slurry; and then coating the surface of the current collector with a coating, and curing to obtain a finished product. Based on the scheme, the performance requirement on the slurry is greatly reduced, the content of the inorganic ion sieve adsorbent in the slurry is greatly increased, the dosage of the organic binder is greatly reduced, the advantage of high specific surface of the inorganic ion sieve adsorbent is reserved, and the adsorption capacity and adsorption rate of the finished film are improved.
2. According to the lithium extraction method, the thin film is used as an electrode and is loaded into the separation type electrochemical device, rapid and efficient lithium removal is achieved through electrochemical reaction, compared with the existing acid leaching lithium removal method, a large amount of practical use is avoided, and the lithium desorption process is completed in the separation type pure device, so that pollutants such as waste residues, waste and the like are not generated.
3. The lithium extraction method provided by the invention realizes continuous adsorption and desorption of lithium ions in salt lake brine, effectively improves the lithium extraction and lithium removal efficiency, and can realize large-scale industrial continuous production.
Drawings
FIG. 1 is a schematic view of an electrolytic cell in an embodiment of the invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and the detailed description, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
The invention discloses a preparation method of a film for extracting lithium from salt lake brine, which comprises the following steps:
(1) Mixing an inorganic ion sieve adsorbent, a conductive additive organic binder and an organic solvent to obtain slurry;
Specifically, the organic ion sieve, the organic binder, the conductive additive and the organic solvent can be directly and uniformly mixed to obtain slurry; the slurry may be obtained by mixing the organic binder with the organic solvent and then uniformly mixing the mixture with the inorganic ion sieve adsorbent and the conductive additive, but is not limited thereto. Preferably, the organic binder and the organic solvent are uniformly mixed, and then the organic binder, the inorganic ion sieve adsorbent and the conductive additive are uniformly mixed.
Wherein, the inorganic ion sieve adsorbent is selected from one or more of titanium ion sieve adsorbent, manganese ion sieve adsorbent, chromium-containing lithium ion sieve adsorbent, aluminum-based lithium adsorbent and antimonate lithium adsorbent; but is not limited thereto.
Specifically, the titanium ion sieve adsorbent may be an adsorbent synthesized by a template method for Li 4Ti5O12、H4Ti5O12 or an adsorbent synthesized by a template method for Li 2TiO、H2TiO3, but is not limited thereto.
Specifically, the manganese-based ion sieve adsorbent may be an adsorbent synthesized by solid phase sintering of LiMn 2O4、HMn2O4, an adsorbent synthesized by solid phase sintering of Li 4Mn5O12、H4Mn5O12, or an adsorbent synthesized by hydrothermal method of Li 1.51Mn1.63O4、H1.36Li0.07Mn1.65O4, but is not limited thereto.
In particular, the chromium-containing lithium ion sieve adsorbent may be, but is not receptive to, li 2Cr(PO4)1.67 and other structurally similar chromium lithium phosphate salts.
Specifically, the aluminum-based lithium adsorbent may be an adsorbent formed by reacting a lithium salt such as licl.2al (OH) 3·nH2 O with amorphous aluminum hydroxide, but is not limited thereto.
Specifically, the antimonate lithium adsorbent may be an adsorbent synthesized by a template method of Li [ Sb (OH) 6 ] and HSbO 3·0.12H2 O, but is not limited thereto.
Preferably, in one embodiment of the present invention, the inorganic ion sieve adsorbent is a titanium ion sieve; more preferred is an adsorbent synthesized from Li 4Ti5O12、H4Ti5O12 by a template method, which has a large adsorption capacity for Li and is more easily uniformly dispersed in the slurry.
Wherein, the organic binder is one or more of PVDF, PEO, PTFE, PAN, PI, PAA, PVA, sodium alginate, styrene-butadiene rubber and SBS, SEBS, NBR, HNBR; but not absorbed. Preferably, the organic binder is PVDF and/or PVA; the binder has less effect on the specific surface area of the inorganic ion sieve adsorbent.
Wherein, the conductive additive is one or more of SuperP, carbon black and carbon nano tube, which can accelerate the electrochemical lithium removal rate and improve the lithium extraction efficiency.
Wherein, the weight ratio of the inorganic ion sieve adsorbent, the conductive additive and the organic binder is (80-98): (1-5) 1-20); ) Exemplary are 83:2:15, 86:2:12, 87:4:9, 90:3:7, 93:4:3, or 97:1:2, but is not limited thereto. Preferred are (84 to 90): (4-5) (10-16). Based on the proportion, the coating with uniform thickness of the post-sizing agent on the surface of the current collector can be ensured; and the adverse effect of the organic binder on the inorganic ion sieve adsorbent can be effectively reduced, so that the lithium extraction capacity and rate can be effectively improved. More preferably, the weight ratio of inorganic ion sieve adsorbent, conductive additive to organic binder is 85:5:10.
Wherein, the organic solvent is selected from one or more of NMP, DMF, toluene, xylene, n-heptane, cyclohexane, ethanol and isopropanol, but is not limited thereto. NMP and/or xylene are preferably selected.
Specifically, the content of the organic solvent in the slurry is 40 to 60wt%, and exemplary is 42wt%, 45wt%, 48wt%, 51wt%, 53wt%, 58wt% or 59wt%, but not limited thereto. Preferably 40 to 46wt%.
The invention adopts the technical scheme that the slurry is coated on the surface of the solid current collector film, so that the requirement on the slurry is low. Therefore, the inorganic ion sieve adsorbent content in the slurry is improved, and the overall adsorption capacity is also improved without adding modifiers such as surfactants and leveling agents into the slurry. The content of the organic binder in the slurry is lower, so that the content of the inorganic ion sieve adsorbent is further improved, the adverse effect of the organic binder on the specific surface area of the inorganic ion sieve powder is reduced, and the adsorption capacity and the adsorption rate are improved.
(2) Forming a coating on the surface of the current collector by adopting slurry, and curing to obtain a finished product;
Specifically, spin coating, blade coating, and the like may be used to form the coating. Preferably, the slurry is scraped on the surface of a current collector, and a coating with the thickness of 50-120 mu m is formed on the surface of the current collector, and the finished product is obtained after heating and curing.
The current collector is a solid film, and can be a metal foil, a semiconductor foil or a conductive nonmetallic film, but is not limited thereto.
Specifically, the metal foil may be copper foil, aluminum foil, stainless steel foil, silver foil, gold foil, etc., but is not limited thereto. The nonmetallic thin film may be a carbon fiber thin film, but is not limited thereto.
Correspondingly, the invention also discloses a film for extracting lithium from salt lake brine, which is prepared by adopting the preparation method.
Correspondingly, the invention also discloses a method for extracting lithium from salt lake brine, which comprises the following steps:
(1) Placing the film into brine, and adsorbing for a preset time;
Wherein, the brine of the invention is dew with high magnesium-lithium ratio, and the Mg/Li (weight) is 10-20. Specifically, in one embodiment of the invention, the brine contains 30-50 Mg/L of Li +, 230-250 Mg/L of Na +, 400-480 Mg/L of K +, 490-550 Mg/L of Mg 2+ and 500-600 Mg/L of Ca 2+.
Specifically, in one embodiment of the present invention, the film is immersed in brine for 6-48 hours, taken out, washed and dried.
(2) And removing lithium ions in the absorbed film.
Specifically, the lithium ion removal may be performed by a conventional process, such as soaking with a strong acid, but is not limited thereto. Preferably, in one embodiment of the invention, the following method is used for delithiation:
(2.1) placing the absorbed film into an electrolytic cell, and carrying out electrolytic reaction by taking the absorbed film as a cathode;
Referring to fig. 1, in one embodiment of the invention, an electrolytic cell comprises a power source 1, an electrolytic cell 2, an ion permeable membrane 3 and an electrode receptacle 4; the electrolytic tank 1 is divided into an A electrolytic tank 21 and a B electrolytic tank 22 by an ion permeable membrane 4, the electrode jack comprises a cathode electrode jack 41 and an anode electrode jack 42, the cathode electrode jack 41 is arranged in the A electrolytic tank 21, the anode electrode jack 42 is arranged in the B electrolytic tank 22, the anode of the power supply 1 is communicated with the anode electrode jack 41, and the cathode of the power supply 1 is communicated with the cathode electrode jack 42. The same solvent or acid electrolyte is contained in both the a cell 21 and the B cell 22. Specifically, the acidic electrolyte is one or more of sulfuric acid, hydrochloric acid, hexafluorophosphoric acid and lithium bistrifluoro methanesulfonimide; but is not limited thereto. One or more of EC, DMC, DEC, EMC, PC and water are selected as the solvent, but not limited thereto. Wherein the ion permeable membrane 3 is permeable to hydrogen ions.
Specifically, when the electrolytic cell performs primary reaction, the positive electrode material of the lithium ion battery is used as the anode. The film after one electrolysis reaction is used as anode.
(2.2) Transferring the film after the electrolytic reaction to an anode of an electrolytic cell, and taking another new film after the adsorption as a cathode to perform the electrolytic reaction; after the electrolytic reaction is finished, the film of the anode is used for removing lithium ions and absorbing salt lake brine as a new film; and obtaining a lithium ion-rich solution in an electrolytic cell where the anode is positioned.
Preferably, an electrolyte replacing device 5 is also connected to one side of the electrolytic tank 21 of the electrolytic tank A, and comprises an original electrolyte tank 51 and a lithium-rich electrolyte tank 52. After the reaction proceeds to a certain extent, the solution rich in lithium ions in the a electrolytic tank 21 may be extracted into the lithium-rich electrolytic tank 52, and then the original electrolyte in the original electrolytic tank 51 may be fed into the a electrolytic tank 21, followed by the subsequent lithium extraction step.
The principle of lithium desorption will be described below using the ion sieve Li 4Ti5O12 as an example. Specifically, in the first reaction of the electrolytic cell, lithium cobaltate is used as an anode (prepared by coating lithium cobaltate on the surface of an aluminum foil current collector), and a film after brine absorption is used as a cathode in the invention, in the step (2.1), the two electrodes react as follows:
And (3) cathode: li (Li) 4Ti5O12+3e-+H+→Li4H3Ti5O12
Anode: liCoO 2→Li1-xCoO2+xLi++xe-
After the completion of the reaction, the flow of electricity is stopped and the anode is pulled out in step (2.2). The thin film of the cathode is pulled out and inserted into an anode socket, and another original electrode (the thin film after absorbing brine) is inserted into the cathode socket to serve as the cathode. Then, a power supply is externally connected and the two electrodes are electrified to work, and the two electrodes react as follows:
And (3) cathode: li (Li) 4Ti5O12+3e-+H+→Li4H3Ti5O12
Anode ：Li4H3Ti5O12→LiH3Ti5O12+3Li++3e-
Thus, the desorption of Li in the film is completed.
The invention is illustrated below by means of specific examples:
Example 1 film for lithium extraction from salt lake brine
The preparation method of the film comprises the following steps:
(1) Dispersing PVDF into DMF to form uniform dispersion, then adding Li 4Ti5O12 lithium ion sieve and SuperP, and uniformly mixing to obtain slurry; wherein the DMF content of the slurry is 40wt%; the mass ratio of the Li 4Ti5O12 lithium ion sieve to the SuperP to the PVDF is 81:1:18;
(2) The slurry is scraped to the surface of a tiled copper foil (solid with the thickness of 80 mu m) by a scraper, the solvent is heated and dried, the slurry is scraped to the other surface of the copper foil, and the solvent is heated and dried to obtain the film. Wherein, the thickness of the film surface coating is 100 μm.
Example 2 film for extraction of lithium from salt lake brine
The preparation method of the film comprises the following steps:
(1) Dispersing PVDF into NMP to form uniform dispersion, then adding Li 4Ti5O12 lithium ion sieve and SuperP, and uniformly mixing to obtain slurry; wherein the DMF content of the slurry is 60wt%; the mass ratio of the Li 4Ti5O12 lithium ion sieve to the SuperP to the PVDF is 98:1:1, a step of;
(2) The slurry is scraped to the surface of a tiled copper foil (solid with the thickness of 80 mu m) by a scraper, the solvent is heated and dried, the slurry is scraped to the other surface of the copper foil, and the solvent is heated and dried to obtain the film. Wherein, the thickness of the film surface coating is 100 μm.
Example 3 film for lithium extraction from salt lake brine
The preparation method of the film comprises the following steps:
(1) Dispersing PVA into DMF to form uniform dispersion, then adding Li 4Ti5O12 lithium ion sieve and SuperP, and uniformly mixing to obtain slurry; wherein the NMP content in the slurry is 40wt%; the mass ratio of the Li 4Ti5O12 lithium ion sieve to the SuperP to the PVA is 81:1:18;
(2) The slurry is scraped to the surface of a tiled copper foil (solid with the thickness of 80 mu m) by a scraper, the solvent is heated and dried, the slurry is scraped to the other surface of the copper foil, and the solvent is heated and dried to obtain the film. Wherein, the thickness of the film surface coating is 100 μm.
Example 4 film for lithium extraction from salt lake brine
The preparation method of the film comprises the following steps:
(1) Dispersing PTFE into NMP to form a uniform dispersion, then adding a Li 4Ti5O12 lithium ion sieve and SuperP, and uniformly mixing to obtain slurry; wherein the NMP content in the slurry is 45wt%; the mass ratio of the Li 4Ti5O12 lithium ion sieve to the SuperP to the PTFE is 88:3:9, a step of performing the process;
(2) The slurry is scraped to the surface of a tiled copper foil (solid with the thickness of 80 mu m) by a scraper, the solvent is heated and dried, the slurry is scraped to the other surface of the copper foil, and the solvent is heated and dried to obtain the film. Wherein, the thickness of the film surface coating is 100 μm.
Test example 1
Lithium adsorption experiments were performed using the films prepared in examples 1 to 4, and the specific procedures are as follows:
A plurality of films were prepared in each example and comparative example, the films were immersed in brine (Li + concentration 40mg L -1Mg2+ concentration 500mg L -1) for 2-16 hours, after 2 hours, one of the films in each example and comparative example was taken out every 1 hour, washed with clear water, dried, weighed, and the absorption rate was calculated.
In addition, at least 1 piece of film was remained in each of the films prepared in examples 1 to 4 and comparative example 1, and the test was performed (weighing once every 1 hour) until the weight change of the film was not more than 0.5% after the two times before and after, the weight of the film was recorded, and the amount of the fully saturated adsorption was calculated. Specific test data are as follows:
Example 5 lithium extraction method
(1) Films were prepared by the methods of examples 1 to 4;
(2) Putting the film into brine, soaking for 36 hours, taking out, washing with clear water, and airing;
(3) Placing the absorbed film into an electrolytic cell, and carrying out electrolytic reaction by taking the absorbed film as a cathode;
Wherein the electrolytic cell comprises a power supply, an electrolytic cell, an ion permeable membrane and an electrode socket; the electrolytic tank is divided into an A electrolytic tank and a B electrolytic tank by an ion permeable membrane, the electrode socket comprises a cathode electrode socket and an anode electrode socket, the cathode electrode socket is arranged in the A electrolytic tank, the anode electrode socket is arranged in the B electrolytic tank, the anode of the power supply is communicated with the anode, and the cathode of the power supply is communicated with the cathode. Sulfuric acid with the concentration of 50wt% is contained in the electrolytic tank A and the electrolytic tank B, and the ion permeable membrane can permeate hydrogen ions.
Specifically, lithium cobaltate is used as an anode when the electrolytic cell performs the primary reaction. The film after one electrolysis reaction is used as anode.
(4) Transferring the film after the electrolytic reaction to an anode of an electrolytic cell, and taking another new film after the adsorption as a cathode to carry out the electrolytic reaction; after the electrolytic reaction is finished, the film of the anode is used for removing lithium ions and absorbing salt lake brine as a new film; and obtaining a lithium ion-rich solution in an electrolytic cell where the anode is positioned.
The desorption rates of examples 1 to 4 were counted, and the specific values are shown in the following table:
desorption rate x 10 -4/g·h-1·cm-2
Example 1 1.79
Example 2 2.14
Example 3 2.44
Example 4 2.62
The above embodiments can show that the film prepared by adopting the technical scheme of the invention can effectively improve the adsorption rate, desorption rate and adsorption capacity of the extracted lithium.
Test example 2
The film prepared in example 4 was used for lithium adsorption and desorption experiments, and the specific method was as in example 5, and the method was repeated 10 times, and the total saturated adsorption amount was recorded each time.
And soaking and desorbing with sulfuric acid (0.45 mol/L), circulating for 10 times, and recording the full saturated adsorption amount each time. The specific table is shown below:
As can be seen from the above table, after the electrochemical desorption, the adsorption capacity of the film after 10 cycles still reaches 99.0% of the initial adsorption capacity, while the acid leaching desorption is adopted, and the adsorption capacity of the film after 10 cycles is 67.5% of the initial adsorption capacity, which indicates that the cycle performance of the film is greatly improved by adopting an electrochemical method.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.

Claims (7)

1. The method for extracting lithium from salt lake brine is characterized by comprising the following steps of:
(1) Placing a film for extracting lithium from salt lake brine into the brine, and adsorbing for a preset time;
(2) Placing the absorbed film into an electrolytic cell, and carrying out electrolytic reaction by taking the absorbed film as a cathode;
(3) Transferring the film after the electrolytic reaction to an anode of an electrolytic cell, and taking another new film after the adsorption as a cathode to carry out the electrolytic reaction; after the electrolytic reaction is finished, the film of the anode is used for removing lithium ions and absorbing salt lake brine as a new film; obtaining a lithium ion-rich solution in an electrolytic cell where an anode is positioned; the electrolytic cell comprises a power supply, an electrolytic cell, an ion permeable membrane and an electrode socket, wherein the ion permeable membrane is arranged in the electrolytic cell, and the electrode socket is used for inserting a thin film;
The preparation method of the film for extracting lithium from salt lake brine comprises the following steps:
(i) Mixing an inorganic ion sieve adsorbent, a conductive additive organic binder and an organic solvent to obtain slurry; wherein the content of the organic solvent in the slurry is 40-60 wt%, and the weight ratio of the inorganic ion sieve adsorbent, the conductive additive and the organic binder is (80-98): (1-5): (1-20); the inorganic ion sieve adsorbent is one or more of titanium ion sieve adsorbent, manganese ion sieve adsorbent, chromium-containing lithium ion sieve adsorbent, aluminum-based lithium adsorbent and antimonate lithium adsorbent;
(ii) Forming a coating on the surface of the current collector by adopting the slurry, and curing to obtain a finished product;
wherein, the current collector is selected from metal foil, semiconductor foil and conductive nonmetallic film.
2. The method for extracting lithium from salt lake brine according to claim 1, wherein the organic binder is one or more selected from PVDF, PEO, PTFE, PAN, PI, PAA, PVA, sodium alginate, styrene-butadiene rubber and SBS, SEBS, NBR, HNBR;
The conductive additive is one or more of SuperP, carbon black and carbon nano tubes;
The organic solvent is selected from one or more of NMP, DMF, toluene, xylene, n-heptane, cyclohexane, ethanol and isopropanol.
3. The method for extracting lithium from salt lake brine according to claim 1, wherein the inorganic ion sieve adsorbent is a titanium ion sieve;
the organic binder is PVDF and/or PVA;
the organic solvent is NMP and/or xylene.
4. The method for extracting lithium from salt lake brine according to claim 1, wherein in the step (2), the slurry is scraped on the surface of a current collector, and a coating with the thickness of 50-120 μm is formed on the surface of the current collector, and the finished product is obtained after heating and curing.
5. The method for extracting lithium from salt lake brine according to claim 1, wherein an acidic electrolyte or a solvent is arranged in the electrolytic tank;
the acidic electrolyte is one or more of sulfuric acid, hydrochloric acid, hexafluorophosphoric acid and lithium bis (trifluoromethanesulfonyl) imide;
The solvent is one or more of EC, DMC, DEC, EMC, PC and water.
6. The method for extracting lithium from salt lake brine according to claim 1, wherein in the step (1), the film for extracting lithium from salt lake brine is immersed in brine, taken out after being immersed for 6-48 hours, and dried after being washed.
7. The method for extracting lithium from salt lake brine according to claim 1, wherein in the step (2), the positive electrode material of the lithium ion battery is used as the anode when the electrolytic cell performs the primary reaction.
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