CN115624958A - Film for extracting lithium from salt lake brine, preparation method of film and lithium extraction method - Google Patents
Film for extracting lithium from salt lake brine, preparation method of film and lithium extraction method Download PDFInfo
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- CN115624958A CN115624958A CN202211164706.2A CN202211164706A CN115624958A CN 115624958 A CN115624958 A CN 115624958A CN 202211164706 A CN202211164706 A CN 202211164706A CN 115624958 A CN115624958 A CN 115624958A
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- lithium
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- salt lake
- lake brine
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 74
- 239000012267 brine Substances 0.000 title claims abstract description 51
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000605 extraction Methods 0.000 title abstract description 20
- 239000010408 film Substances 0.000 claims abstract description 73
- 239000003463 adsorbent Substances 0.000 claims abstract description 61
- 239000002002 slurry Substances 0.000 claims abstract description 44
- 238000001179 sorption measurement Methods 0.000 claims abstract description 36
- 239000011230 binding agent Substances 0.000 claims abstract description 26
- 229910001410 inorganic ion Inorganic materials 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 239000010409 thin film Substances 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000002482 conductive additive Substances 0.000 claims abstract description 16
- 239000011888 foil Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 5
- 239000004065 semiconductor Substances 0.000 claims abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 33
- 229910001416 lithium ion Inorganic materials 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- -1 hydrogen ions Chemical class 0.000 claims description 4
- 229910001437 manganese ion Inorganic materials 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229920006168 hydrated nitrile rubber Polymers 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012466 permeate Substances 0.000 claims description 3
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 3
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 24
- 239000010936 titanium Substances 0.000 description 20
- 238000003795 desorption Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 230000006872 improvement Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007970 homogeneous dispersion Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- DTDBPEHSXDRASZ-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Cr+3].[Li+] Chemical class P(=O)([O-])([O-])[O-].[Cr+3].[Li+] DTDBPEHSXDRASZ-UHFFFAOYSA-K 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 210000003719 b-lymphocyte Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a thin film for extracting lithium from salt lake brine, a preparation method of the thin film 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 using the slurry, and curing to obtain a finished product; the current collector is made of metal foil, semiconductor foil and conductive non-metal film. The invention can improve the adsorption capacity and adsorption rate of the film, and improve the lithium quantity and lithium extraction efficiency.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a thin film for extracting lithium from salt lake brine, a preparation method of the thin film and a lithium extraction method.
Background
The lithium extraction from 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 lithium extraction yield from the salt lake brine in the total yield of the lithium salt is lower in China. The main reason is that the salt lake brine in China has high magnesium-lithium ratio and high lithium extraction difficulty. The adsorption method has great advantages in economy and environmental protection aiming at the brine with high magnesium-lithium ratio and low lithium concentration, and the method has the advantages of relatively simple process, low energy consumption, high recovery rate and good selectivity, and is a preferable process scheme. The adsorbents (ion sieves) used in the adsorption process are generally classified into organic adsorbents and inorganic adsorbents.
The organic adsorbent mainly studies crown ether, and the application is limited due to higher cost at present. The inorganic adsorbent is mainly divided into a manganese-containing adsorbent, a titanium-containing adsorbent, an aluminum-containing adsorbent, a lithium antimonate adsorbent and the like, and has high selectivity. The principle is as follows: composite lithium-containing metal oxides are produced by calcination and then the lithium of the oxide is replaced by hydrogen by a strong acid-soaked ion exchange reaction. The acid-leached oxide can be used for extracting lithium in low brine concentration again through ion exchange reaction. And the desorption of lithium ions is realized by acid leaching the ion sieve after the extraction of lithium again. The inorganic adsorbent has high selectivity and is very suitable for extracting lithium ions in brine with high magnesium-lithium ratio. However, the inorganic ion sieve powder has the problems of small particle size and poor fluidity, and the contradiction between powder loss and difficult recycling can occur in industrial application. In order to solve such a problem, a common method for improving the adsorption performance of the powder is to granulate the powder and then adsorb the powder, or to prepare the powder into slurry and then to hang the powder on a net-shaped film. However, in these improvement processes, a large amount of organic binders, surfactants and other auxiliary agents need to be added, the adsorption capacity and the ion exchange rate are reduced, the operation period is greatly increased, continuous production cannot be performed, and huge equipment needs to be used.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a thin film for extracting lithium from salt lake brine, wherein the prepared thin film has high adsorption capacity and adsorption rate, and can effectively improve the lithium extraction efficiency.
The invention also aims to solve the technical problem of providing a film for extracting lithium from salt lake brine, which has high adsorption capacity and adsorption rate and can effectively improve the lithium extraction efficiency.
The invention also aims to solve 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 thin 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 using the slurry, and curing to obtain a finished product;
the current collector is made of metal foil, semiconductor foil and conductive non-metal film.
As an improvement of the above technical solution, the inorganic ion sieve adsorbent is one or more of a titanium ion sieve adsorbent, a manganese ion sieve adsorbent, a chromium-containing lithium ion sieve adsorbent, an aluminum-based lithium adsorbent, and an antimonate lithium adsorbent;
the organic binder is one or more of PVDF, PEO, PTFE, PAN, PI, PAA, PVA, sodium alginate, styrene-butadiene rubber, SBS, SEBS, NBR and HNBR;
the conductive additive is one or more of SuperP, carbon black and carbon nano tubes;
the organic solvent is 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 coated on the surface of the current collector in a scraping way, a coating with the thickness of 50-120 mu m is formed on the surface of the current collector, and a 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) Putting the film into brine, and adsorbing for a preset time;
(2) And removing lithium ions in the adsorbed film to obtain the lithium ion battery.
As an improvement of the technical scheme, the step (2) comprises the following steps:
(2.1) putting the adsorbed film into an electrolytic cell, and taking the adsorbed film as a cathode to perform electrolytic reaction;
(2.2) transferring the film after the electrolytic reaction to an anode of an electrolytic cell, and taking another new film after adsorption as a cathode to perform the electrolytic reaction; after the electrolysis reaction is finished, the film of the anode finishes the lithium ion removal and is used as a new film for absorbing the brine; obtaining a lithium ion-rich solution in an electrolytic cell in which the anode is positioned;
the electrolytic cell comprises a power supply, an electrolytic cell, an ion permeable membrane arranged in the electrolytic cell and an electrode jack used for inserting the membrane, wherein the ion permeable membrane can permeate hydrogen ions.
As an improvement of the technical scheme, an acidic electrolyte or a solvent is arranged in the electrolytic cell;
the acid electrolyte is one or more of sulfuric acid, hydrochloric acid, hexafluorophosphoric acid and lithium bistrifluoromethanesulfonimide;
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, taken out after being immersed for 6-48h, and dried after being rinsed.
As an improvement of the above technical solution, in the step (2.1), the lithium ion battery cathode material is used as the anode in the initial reaction of the electrolytic cell.
The implementation of the invention has the following beneficial effects:
1. the preparation method of the film for extracting lithium from salt lake brine comprises the following steps of mixing an inorganic ion sieve adsorbent, a conductive additive, an organic binder and an organic solvent into slurry; and then coating the mixture on the surface of the current collector to form a coating, and curing to obtain a finished product. Based on the scheme, the performance requirement on the slurry is greatly reduced, so that the content of the inorganic ion sieve adsorbent in the slurry is greatly increased, the using amount of the organic binder is greatly reduced, the advantage of high specific surface area of the inorganic ion sieve adsorbent is reserved, and the adsorption capacity and the adsorption rate of the finished film are improved.
2. The lithium extraction method provided by the invention has the advantages that the thin film is used as an electrode and loaded into the separated electrochemical device, the rapid and efficient lithium removal is realized through the electrochemical reaction, compared with the existing acid leaching lithium removal method, the practicability of large amount calculation is avoided, the lithium desorption process is completed in the separated pure device, and pollutants such as waste residues and wastes 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 removal efficiency, and can realize large-scale industrial continuous production.
Drawings
FIG. 1 is a schematic illustration of an electrolytic cell in one embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and detailed description.
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; or, the organic binder and the organic solvent may be mixed first, and then the mixture is uniformly mixed with the inorganic ion sieve adsorbent and the conductive additive to obtain the slurry, but the invention 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 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 Li 4 Ti 5 O 12 、H 4 Ti 5 O 12 The adsorbent synthesized by the template method can also be Li 2 TiO、H 2 TiO 3 The adsorbent is synthesized by a template method, but is not limited thereto.
Specifically, the manganese ion sieve adsorbent can be LiMn 2 O 4 、HMn 2 O 4 Adsorbent synthesized by solid phase sintering, and method for producing the same 4 Mn 5 O 12 、H 4 Mn 5 O 12 Adsorbent synthesized by solid phase sintering, and method for producing the same 1.51 Mn 1.63 O 4 、H 1.36 Li 0.07 Mn 1.65 O 4 But not limited to, an adsorbent synthesized by a hydrothermal method.
Specifically, the chromium-containing lithium ion sieve adsorbent can be Li 2 Cr(PO4) 1.67 And other lithium chromium phosphates of similar structure, but not absorbed therewith.
Specifically, the aluminum-based lithium adsorbent can be LiCl.2Al (OH) 3 ·nH 2 Lithium salts such as O and the like and amorphous aluminum hydroxide, but is not limited thereto.
Specifically, the lithium antimonate adsorbent may be Li [ Sb (OH) 6 ]And HSbO 3 ·0.12H 2 The adsorbent is synthesized by a template method, but is not limited to the method.
Preferably, in one embodiment of the present invention, the inorganic ion sieve adsorbent is a titanium ion sieve; more preferably from Li 4 Ti 5 O 12 、H 4 Ti 5 O 12 Sorbents synthesized by templatingThe adsorbent has large adsorption capacity to Li and is easier to be 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, SBS, SEBS, NBR and HNBR; but does not accommodate this. Preferably, the organic binder is PVDF and/or PVA; such a binder has less influence on the specific surface area of the inorganic ion sieve adsorbent.
The conductive additive is one or more of SuperP, carbon black and carbon nano tubes, so that the electrochemical lithium removal rate can be increased, and the lithium extraction efficiency is improved.
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 is 83:2, but is not limited thereto. Preferred are (84 to 90): (4-5) (10-16). Based on the proportion, the slurry can form a coating with uniform thickness on the surface of the current collector in the later period; but also can effectively reduce the adverse effect of the organic binder on the inorganic ion sieve adsorbent, thereby effectively improving the lithium extraction capacity and speed. More preferably, the weight ratio of the inorganic ion sieve adsorbent, the conductive additive and the organic binder is 85:5:10.
wherein, the organic solvent is 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 used.
Specifically, the content of the organic solvent in the slurry is 40 to 60wt%, illustratively 42wt%, 45wt%, 48wt%, 51wt%, 53wt%, 58wt%, or 59wt%, but is not limited thereto. Preferably 40 to 46wt%.
The technical scheme adopted by the invention is to form a coating on the surface of the solid current collector film by the slurry, which has low requirements on the slurry. Therefore, modifying agents such as a surfactant and a leveling agent do not need to be added into the slurry, so that the content of the inorganic ion sieve adsorbent in the slurry is increased, and the overall adsorption amount is also increased. And 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 the slurry, and curing to obtain a finished product;
specifically, the coating layer can be formed by spin coating, doctor blading, or the like. Preferably, the slurry is coated on the surface of the current collector in a blade mode, a coating with the thickness of 50-120 mu m is formed on the surface of the current collector, and a finished product is obtained after heating and curing.
The current collector is a thin film with a solid structure, and specifically, a metal foil, a semiconductor foil, and a conductive non-metal thin film can be used, but 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 non-metal film may be a carbon fiber 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) Putting the film into brine, and adsorbing for a preset time;
wherein, the brine is dew with high magnesium-lithium ratio, and the Mg/Li (weight) is 10-20. Specifically, in one embodiment of the invention, in brine, li + The content is 30-50 mg/L, na + The content is 230-250 mg/L, K + The content of (A) is 400-480 Mg/L, mg 2+ The content of (A) is 490-550 mg/L, ca 2+ The content of (A) is 500-600 mg/L.
Specifically, in one embodiment of the invention, the film is immersed in brine, taken out after being immersed for 6-48h, washed and dried.
(2) And removing lithium ions in the adsorbed film.
Specifically, the lithium ion removal can be performed by a conventional process, such as soaking with a strong acid, but not limited thereto. Preferably, in one embodiment of the present invention, the following method is used for delithiation:
(2.1) putting the adsorbed film into an electrolytic cell, and taking the adsorbed film as a cathode to perform electrolytic reaction;
referring to fig. 1, in one embodiment of the invention, the electrolytic cell comprises a power supply 1, an electrolytic bath 2, an ion permeable membrane 3 and electrode sockets 4; the electrolytic bath 1 is divided into an A electrolytic bath 21 and a B electrolytic bath 22 by an ion permeable membrane 4, the electrode sockets comprise a cathode electrode socket 41 and an anode electrode socket 42, the cathode electrode socket 41 is arranged in the A electrolytic bath 21, the anode electrode socket 42 is arranged in the B electrolytic bath 22, the anode of the power supply 1 is communicated with the anode electrode socket 41, and the cathode of the power supply 1 is communicated with the cathode electrode socket 42. The same solvent or acidic electrolyte is contained in 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 bistrifluoromethanesulfonimide; but is not limited thereto. The solvent is selected from one or more of EC, DMC, DEC, EMC, PC, and water, but is not limited thereto. A membrane in which the ion-permeable membrane 3 is permeable to hydrogen ions.
Specifically, when the electrolytic cell performs the initial reaction, the anode material of the lithium ion battery is used as the anode. And then taking the film subjected to the primary electrolytic reaction as an anode.
(2.2) transferring the film after the electrolytic reaction to an anode of an electrolytic cell, and taking another new film after adsorption as a cathode to carry out the electrolytic reaction; after the electrolysis reaction is finished, the film of the anode finishes the lithium ion removal and is used as a new film for the adsorption of salt lake brine; the anode is in the electrolytic cell to obtain a lithium ion rich solution.
Preferably, an electrolyte replacing device 5 is also connected to one side of the electrolytic bath 21 of the electrolytic cell A, and comprises an original electrolyte bath 51 and a lithium-rich electrolyte bath 52. When the reaction has proceeded to a certain extent, the lithium ion-rich solution in the a electrolytic tank 21 can be pumped out to the lithium-rich electrolytic tank 52, the original electrolytic solution in the original electrolytic tank 51 can be replenished into the a electrolytic tank 21, and then the subsequent lithium extraction step can be performed.
Below with an ionic sieve Li 4 Ti 5 O 12 For example, the principle of lithium desorption will be explained.Specifically, when the electrolytic cell is subjected to the primary reaction, lithium cobaltate is used as an anode (prepared by coating lithium cobaltate on the surface of an aluminum foil current collector), and the thin film adsorbing brine is used as a cathode, in the step (2.1), the reactions of the two electrodes are as follows:
cathode: li 4 Ti 5 O 12 +3e - +H + →Li 4 H 3 Ti 5 O 12
Anode: liCoO 2 →Li 1-x CoO 2 +xLi + +xe -
After the reaction, the procedure proceeds to step (2.2), and the energization is stopped to pull out the anode. And pulling out the membrane of the cathode, inserting the membrane into the anode socket, and inserting another original electrode (the membrane after brine adsorption) on the cathode socket to serve as the cathode. Then, the power supply is connected externally and electrified to work, and the two electrodes react as follows:
cathode: li 4 Ti 5 O 12 +3e - +H + →Li 4 H 3 Ti 5 O 12
Anode: li 4 H 3 Ti 5 O 12 →LiH 3 Ti 5 O 12 +3Li + +3e -
Thus, the desorption of Li from the thin film is completed.
The invention is illustrated below in specific examples:
example 1 thin film for extracting lithium from salt lake brine
The preparation method of the film comprises the following steps:
(1) PVDF is dispersed in DMF to form a homogeneous dispersion, and then Li is added 4 Ti 5 O 12 Uniformly mixing the lithium ion sieve and the SuperP to obtain slurry; wherein, the content of DMF in the slurry is 40wt%; li 4 Ti 5 O 12 The mass ratio of the lithium ion sieve to the SuperP to the PVDF is 81:1:18;
(2) And (3) coating the slurry on the surface of a flat copper foil (solid, with the thickness of 80 mu m) by using a scraper, heating and drying the solvent, coating the slurry on the other surface of the copper foil, and heating and drying the solvent to obtain the film. Wherein the thickness of the thin film surface coating is 100 mu m.
Example 2 film for extracting lithium from salt lake brine
The preparation method of the film comprises the following steps:
(1) PVDF is dispersed in NMP to form a uniform dispersion, and then Li is added 4 Ti 5 O 12 Uniformly mixing the lithium ion sieve and the SuperP to obtain slurry; wherein, the content of DMF in the slurry is 60wt%; li 4 Ti 5 O 12 The mass ratio of the lithium ion sieve to the SuperP to the PVDF is 98:1:1;
(2) And (3) coating the slurry on the surface of a flat copper foil (solid, with the thickness of 80 mu m) by using a scraper, heating and drying the solvent, coating the slurry on the other surface of the copper foil, and heating and drying the solvent to obtain the film. Wherein the thickness of the thin film surface coating is 100 mu m.
Example 3 film for extracting lithium from salt lake brine
The preparation method of the film comprises the following steps:
(1) Dispersing PVA in DMF to form homogeneous dispersion, and adding Li 4 Ti 5 O 12 Uniformly mixing the lithium ion sieve and the SuperP to obtain slurry; wherein the NMP content in the slurry is 40wt%; li 4 Ti 5 O 12 The mass ratio of the lithium ion sieve to the SuperP to the PVA is 81:1:18;
(2) And (3) coating the slurry on the surface of a flat copper foil (solid, with the thickness of 80 mu m) by using a scraper, heating and drying the solvent, coating the slurry on the other surface of the copper foil, and heating and drying the solvent to obtain the film. Wherein the thickness of the thin film surface coating is 100 mu m.
Example 4 film for extracting lithium from salt lake brine
The preparation method of the film comprises the following steps:
(1) Dispersing PTFE in NMP to form a uniform dispersion, and then adding Li 4 Ti 5 O 12 Uniformly mixing the lithium ion sieve and the SuperP to obtain slurry; wherein the NMP content in the slurry is 45wt%; li 4 Ti 5 O 12 The mass ratio of the lithium ion sieve to the SuperP to the PTFE is 88:3:9;
(2) And (3) coating the slurry on the surface of a flat copper foil (solid, with the thickness of 80 mu m) by using a scraper, heating and drying the solvent, coating the slurry on the other surface of the copper foil, and heating and drying the solvent to obtain the film. Wherein the thickness of the thin film surface coating is 100 mu m.
Test example 1
Lithium adsorption experiments were performed using the films prepared in examples 1-4, as follows:
each of the examples and comparative examples was prepared by preparing a plurality of thin films, and immersing the thin films in brine (Li) + The concentration is 40mg L -1 Mg 2+ The concentration is 500mg L -1 ) After soaking for 2-1693 h, one of the samples in each example and comparative example was taken out every 1h, washed with clean water, dried, weighed, and the absorption rate was calculated.
In addition, the films obtained in each of examples 1 to 4 and comparative example 1 were kept at least 1 piece, and the test was continued (weighing was performed every 1 hour) until the weight change of the film was not more than 0.5% before and after the two times, and then the weight of the film was recorded to calculate the completely saturated adsorption amount. The specific test data are as follows:
example 5 lithium extraction method
(1) Films were prepared by the method of examples 1 to 4;
(2) Putting the film into brine, soaking for 36h, taking out, washing with clear water, and drying in the air;
(3) Putting the adsorbed film into an electrolytic cell, and taking the adsorbed film as a cathode to perform electrolytic reaction;
wherein, the electrolytic cell comprises a power supply, an electrolytic bath, an ion permeable membrane and an electrode socket; the electrolytic bath is divided into an electrolytic bath A and an electrolytic bath B by an ion permeable membrane, the electrode sockets comprise a cathode electrode socket and an anode electrode socket, the cathode electrode socket is arranged in the electrolytic bath A, the anode electrode socket is arranged in the electrolytic bath B, the anode of the power supply is communicated with the anode, and the cathode of the power supply is communicated with the cathode. The A electrolytic cell and the B electrolytic cell are filled with 50wt% sulfuric acid, and the ion permeable membrane can permeate hydrogen ions.
Specifically, the electrolytic cell takes lithium cobaltate as an anode during the initial reaction. And then taking the film subjected to the primary electrolytic reaction as an anode.
(4) Transferring the film after the electrolytic reaction to an anode of an electrolytic cell, and performing electrolytic reaction by taking another new film after adsorption as a cathode; after the electrolysis reaction is finished, the film of the anode finishes the lithium ion removal and is used as a new film for the adsorption of salt lake brine; the anode is in the electrolytic cell to obtain a lithium ion rich solution.
The desorption rates of the examples 1 to 4 were counted, and the following table was used:
| desorption rate X10 -4 /g·h -1 ·cm -2 | |
| Example 1 | 1.79 |
| Example 2 | 2.14 |
| Example 3 | 2.44 |
| Example 4 | 2.62 |
According to the embodiments, the film prepared by the technical scheme of the invention can effectively improve the adsorption rate, desorption rate and adsorption capacity of lithium extraction.
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 cycle was 10 times, and the full saturation adsorption amount was recorded for each time.
And soaking and desorbing with sulfuric acid (0.45 mol/L) for 10 times, and recording the fully saturated adsorption amount of each time. The details are shown in the following table:
it can be seen from the above table that after the electrochemical desorption is adopted, the adsorption capacity of the membrane still reaches 99.0% of the initial adsorption capacity after 10 times of membrane circulation, and after the membrane circulation 10, the adsorption capacity is 67.5% of the initial adsorption capacity by adopting acid leaching desorption, which indicates that the cycle performance of the membrane is greatly improved by adopting the electrochemical method.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a film for extracting lithium from salt lake brine is characterized by comprising 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 using the slurry, and curing to obtain a finished product;
the current collector is made of metal foil, semiconductor foil and conductive non-metal film.
2. The method for preparing the film for extracting lithium from the salt lake brine according to claim 1, wherein the inorganic ion sieve adsorbent is one or more of a titanium ion sieve adsorbent, a manganese ion sieve adsorbent, a chromium-containing lithium ion sieve adsorbent, an aluminum-based lithium adsorbent and an antimonate lithium adsorbent;
the organic binder is one or more of PVDF, PEO, PTFE, PAN, PI, PAA, PVA, sodium alginate, styrene-butadiene rubber, SBS, SEBS, NBR and HNBR;
the conductive additive is one or more of SuperP, carbon black and carbon nano tubes;
the organic solvent is one or more of NMP, DMF, toluene, xylene, n-heptane, cyclohexane, ethanol and isopropanol.
3. The method for preparing the film for extracting lithium from the 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 preparing the thin film for extracting lithium from the salt lake brine according to claim 1, wherein in the step (2), the slurry is blade-coated on the surface of the current collector to form a coating with a thickness of 50-120 μm on the surface of the current collector, and the coating is heated and cured to obtain a finished product.
5. A thin film for extracting lithium from salt lake brine, which is prepared by the preparation method of any one of claims 1 to 4.
6. A method for extracting lithium from salt lake brine is characterized by comprising the following steps:
(1) Placing the membrane of claim 5 in brine and adsorbing for a predetermined time;
(2) And removing lithium ions in the adsorbed film to obtain the lithium ion battery.
7. The method for extracting lithium from salt lake brine of claim 6, wherein the step (2) comprises the following steps:
(2.1) putting the adsorbed film into an electrolytic cell, and taking the adsorbed film as a cathode to perform electrolytic reaction;
(2.2) transferring the film after the electrolytic reaction to an anode of an electrolytic cell, and taking another new film after adsorption as a cathode to perform the electrolytic reaction; after the electrolysis reaction is finished, the film of the anode finishes the lithium ion removal and is used as a new film for the adsorption of salt lake brine; obtaining a lithium ion-rich solution in an electrolytic cell in which the anode is positioned;
the electrolytic cell comprises a power supply, an electrolytic cell, an ion permeable membrane arranged in the electrolytic cell and an electrode jack used for inserting the membrane, wherein the ion permeable membrane can permeate hydrogen ions.
8. The method for extracting lithium from salt lake brine according to claim 7, wherein an acidic electrolyte or a solvent is arranged in the electrolytic cell;
the acid electrolyte is one or more of sulfuric acid, hydrochloric acid, hexafluorophosphoric acid and lithium bistrifluoromethanesulfonimide;
the solvent is one or more of EC, DMC, DEC, EMC, PC and water.
9. The method for extracting lithium from salt lake brine according to claim 6, wherein in the step (1), the film according to claim 5 is immersed in brine, taken out after being soaked for 6-48h, washed and dried.
10. The method for extracting lithium from salt lake brine as claimed in claim 7, wherein in the step (2.1), the lithium ion battery cathode material is used as the anode in the primary reaction of the electrolytic cell.
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