CN117101432A - Lithium ion separation membrane based on intercalation large-size graphene oxide, and preparation method and application thereof - Google Patents
Lithium ion separation membrane based on intercalation large-size graphene oxide, and preparation method and application thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 148
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 239000012528 membrane Substances 0.000 title claims abstract description 86
- 238000000926 separation method Methods 0.000 title claims abstract description 73
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 70
- 238000009830 intercalation Methods 0.000 title claims abstract description 30
- 230000002687 intercalation Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 44
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- 239000000138 intercalating agent Substances 0.000 claims abstract description 24
- 238000000151 deposition Methods 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000011229 interlayer Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 18
- 239000004695 Polyether sulfone Substances 0.000 claims description 17
- 229920006393 polyether sulfone Polymers 0.000 claims description 17
- 238000000967 suction filtration Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010345 tape casting Methods 0.000 claims description 10
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 7
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 4
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 4
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 41
- 239000012267 brine Substances 0.000 abstract description 30
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract description 30
- 238000000605 extraction Methods 0.000 abstract description 29
- 150000002500 ions Chemical class 0.000 abstract description 16
- 150000003839 salts Chemical class 0.000 abstract description 5
- 238000005374 membrane filtration Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 29
- 239000010410 layer Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- -1 graphene oxide salt Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000001728 nano-filtration Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920006284 nylon film Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000409 membrane extraction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000879 optical micrograph Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- 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
- B01D71/02—Inorganic material
- B01D71/021—Carbon
- B01D71/0211—Graphene or derivates thereof
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The application discloses a lithium ion separation membrane based on intercalation large-size graphene oxide, a preparation method and application thereof, and belongs to the technical field of membrane filtration and ion separation. The preparation method comprises the steps of blending graphene oxide solution with an intercalation agent, standing to obtain a mixed solution, depositing the mixed solution on a substrate film, and drying to obtain the brine lithium extraction film. The application of the brine lithium extraction membrane prepared by the graphene oxide-based brine lithium extraction membrane preparation method in brine lithium ion extraction is provided. The interlayer spacing of the graphene oxide film is regulated through the specific intercalating agent, so that the specific ion can be selectively filtered, and the mechanical property and the film forming property of large-size graphene oxide are better improved along with the increase of the size of the graphene oxide, so that the stability of the film can be kept at a thinner film thickness, and the high-selectivity and high-flux stable extraction of lithium ions in salt lakes or brine can be realized.
Description
Technical Field
The application belongs to the technical field of membrane filtration and ion separation, and particularly relates to a lithium ion separation membrane based on intercalation large-size graphene oxide, a preparation method and application thereof.
Background
Lithium metal is recognized as "energy metal which promotes world progress" due to its light weight and high energy density. With the wide application of lithium in the manufacture of power batteries for new energy automobiles, the demand for lithium extraction has also increased greatly in recent years. Wherein, one part of the lithium exists in the form of solid lithium ores such as spodumene, and the other part exists in the form of salt lake lithium. Solid state lithium ores have failed to meet industry's growing demands for lithium due to the distribution topography and low reserves. Therefore, exploration of lithium extraction from salt lakes with abundant reserves is an effective and necessary solution to solve the gap of lithium resources.
The method for extracting lithium from the salt lake commonly used at present comprises the following steps: the solution extraction method, the adsorption method and the membrane separation method have the advantages of complex process flow, high cost, adoption of resin lithium adsorbent in the adsorption method, high cost, low adsorption rate and low recovery efficiency of the adsorbent. In contrast, the membrane separation method has simple process flow, low cost and good efficiency, and the membrane separation method mainly utilizes nanofiltration membranes to separate magnesium and lithium ions in salt lakes, and the nanofiltration membranes can pass monovalent ions and can intercept divalent or multivalent ions due to steric hindrance and the southwest effect. However, nanofiltration membranes have problems such as low flux and retention rate, poor selectivity between monovalent ions, and the like, and often need to be mutually compounded with other adsorbents, so that the cost is high.
Disclosure of Invention
In order to overcome the defects of the prior art, the application aims to provide a lithium ion separation membrane based on intercalation large-size graphene oxide, a preparation method and application thereof, which are used for solving the problems of low lithium flux, low rejection rate and poor membrane performance of membrane extraction.
In order to achieve the above purpose, the application is realized by adopting the following technical scheme:
the application provides a preparation method of a lithium ion separation membrane based on intercalation large-size graphene oxide, which comprises the following steps:
mixing large-size graphene oxide sheets with average size of 5-150 mu m with deionized water to obtain a large-size graphene oxide solution;
and (3) blending the large-size graphene oxide solution with an intercalation agent, standing to obtain a mixed solution, depositing the mixed solution on a substrate film, and drying to obtain the lithium ion separation film.
In the specific implementation process, the concentration of the large-size graphene oxide solution is 0.05-5 mg/ml; the concentration ratio of the large-size graphene oxide solution to the intercalating agent is 1: (0.1-50); the thickness of the large-size graphene oxide sheet is 0.34-10 nm.
In the specific implementation process, the intercalation agent is one or a combination of more of metal ion-containing chloride salt, metal ion-containing hydroxide, tetramethyl ammonium chloride, tetrabutyl ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, 12-crown-4 ether, 15-crown-5 ether and 18-crown-6 ether.
In a specific implementation process, the intercalating agent is positioned between or on the surface of large-size graphene oxide sheets inside the lithium ion separation membrane.
In the specific implementation process, the mode of depositing the mixed solution on the substrate film is any one of knife coating, spin coating and negative pressure suction filtration.
In the specific implementation process, the substrate film is any one of a polyethersulfone film, a nylon film, a mixed cellulose film and an anodic aluminum oxide film.
In the specific implementation process, the temperature of the drying treatment is 20-120 ℃, the humidity of the drying treatment is 10-80%, and the time of the drying treatment is 30 min-2 d.
The application provides a lithium ion separation membrane prepared by the preparation method of the lithium ion separation membrane based on intercalation large-size graphene oxide.
In the specific implementation process, the interlayer spacing of the lithium ion separation membrane is 0.4-5 nm; the thickness of the lithium ion separation membrane is 20 nm-50 mu m.
The application provides a lithium ion separation membrane based on intercalation large-size graphene oxide, which is applied to selective filtration and separation of lithium ions in salt lake water or a salt solution system.
Compared with the prior art, the application has the following beneficial effects:
the application provides a preparation method of a lithium ion separation membrane based on intercalation large-size graphene oxide, wherein large-size graphene oxide sheets are used as ideal two-dimensional materials, and can form regular nanoscale ion transmission channels after being mutually stacked to form a membrane; the problems that the traditional polymer film is low in lithium selectivity, small in treatment capacity, and difficult to solve in film stability and the like when extracting lithium are solved in principle through the large-size graphene oxide film; the interlayer spacing of the graphene oxide membrane is regulated by a specific intercalating agent, so that the selective filtration of specific ions (such as lithium ions) can be realized, and as the size of the graphene oxide is increased, the mechanical property and the film forming property of large-size graphene oxide are better, the stability of the membrane can be improved, and the stability can be kept at a thinner film thickness, so that the high-selectivity and high-flux stable extraction of lithium ions in salt lake water or a salt solution system can be realized.
The lithium ion separation membrane prepared by the application has the advantages of simple process, high lithium ion selectivity, large treatment flux, low cost, no pollution and the like.
The lithium ion separation membrane prepared by the application is applied to selective filtration and separation of lithium ions in salt lake water or salt solution systems, has the advantages of large treatment flux and high retention rate, and does not need to be mutually combined with other adsorbents for use, is different from a common polymer membrane, has accurate and adjustable two-dimensional space between graphene oxide membrane layers, has better selectivity for monovalent ions, and is favorable for selectively extracting lithium in complex salt water environments.
Drawings
FIG. 1 is an optical micrograph of a lithium ion separation membrane based on intercalated large-sized graphene oxide prepared according to the present application;
fig. 2 is a scanning electron micrograph of a lithium ion separation membrane based on intercalated large-sized graphene oxide prepared according to the present application.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present application, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the application in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features such as values, amounts, and concentrations that are defined herein in the numerical or percent ranges are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
Herein, unless otherwise indicated, "comprising," "including," "having," or similar terms encompass the meanings of "consisting of … …" and "consisting essentially of … …," e.g., "a includes a" encompasses the meanings of "a includes a and the other and" a includes a only.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
The application provides a lithium ion separation membrane based on intercalation large-size graphene oxide, a preparation method and application thereof.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The following examples use instrumentation conventional in the art. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. The following examples used various starting materials, unless otherwise indicated, were conventional commercial products, the specifications of which are conventional in the art. In the description of the present application and the following examples, "%" means weight percent, and "parts" means parts by weight, and ratios means weight ratio, unless otherwise specified.
The application provides a preparation method of a lithium ion separation membrane based on intercalation large-size graphene oxide, which comprises the following steps:
step one: taking a large-size graphene oxide solution with an average size of 5-150 mu m and an intercalator according to the following weight ratio of 1: blending the mixture in a concentration ratio of (0.1-50), and standing for 10 min-5 d to obtain a mixed solution; wherein the concentration of the large-size graphene oxide in the large-size graphene oxide solution is 0.05-5 mg/ml; the thickness of the large-size graphene oxide sheet is 0.34-10 nm; the intercalating agent is between or on the surface of the large-sized graphene oxide sheets within the membrane.
The preparation process of the large-size graphene oxide solution comprises the step of mixing large-size graphene oxide sheets with the average size of 5-150 mu m with deionized water to obtain the large-size graphene oxide solution.
In the specific implementation process, the blending means that the large-size graphene oxide and the intercalation agent are combined in a physical mode of stirring, ultrasonic or vibration, so that the intercalation agent is ensured to be positioned between or on the large-size graphene oxide sheets in the lithium ion separation membrane, and the intercalation agent is uniformly attached to the surface of the graphene.
Step two: depositing the mixed solution on any one substrate film of a filter membrane polyether sulfone film, a nylon film, a mixed cellulose film and an anodic aluminum oxide film by means of blade coating, spin coating, negative pressure suction filtration and the like; drying at a certain temperature and humidity to prepare a large-size graphene oxide-based lithium ion separation membrane; the interlayer spacing of the lithium ion separation membrane is 0.4-5 nm, so that the screening capability of different ions is ensured; the thickness is 20 nm-50 μm.
Alternatively, the intercalating agent species comprises one or a combination of several of chloride and hydroxide of various metal ions (sodium, potassium, lithium, magnesium, calcium, aluminium), alkyl ammonium (tetramethyl ammonium chloride, tetrabutyl ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride), crown ether (12-crown-4 ether, 15-crown-5 ether, 18-crown-6 ether).
The temperature of the drying treatment is 20-120 ℃, the humidity is 10-80%, and the drying time is 30 min-2 d.
The lithium ion separation membrane prepared by the application has simple process, high lithium ion selectivity, high treatment flux, low cost and no pollution when being applied to lithium ion extraction.
The lithium ion separation membrane prepared by the application is applied to the selective filtration and separation of lithium ions in salt lake water or salt solution systems, has large treatment flux and high retention rate, has stable membrane performance and does not need to be mutually combined with other adsorbents.
The large-size graphene oxide sheets are taken as ideal two-dimensional materials, and can form regular nanoscale ion transmission channels after being mutually stacked to form films. The problems that the traditional polymer film is low in lithium selectivity, small in treatment capacity, and difficult to solve in film stability and the like when extracting lithium are solved in principle through the large-size graphene oxide film.
And the specific intercalation agent adjusts the interlayer spacing of the graphene oxide film so as to selectively filter specific ions, and along with the increase of the size of the graphene oxide, the migration channels of the ions among the graphene layers are longer and more uniform, thereby being beneficial to accurately screening the ions through the size effect and interlayer action. In addition, the mechanical property and the film forming property can improve the stability of the film, can keep stable when the film thickness is smaller, thereby realizing high-selectivity and high-flux stable extraction of lithium ions in salt lakes or bittern.
Example 1:
the lithium ion separation membrane based on intercalation large-size graphene oxide comprises the following steps: graphene oxide (sheet thickness 1 nm) having an average size of 15 μm was prepared as 100ml of a graphene oxide solution having a concentration of 1mg/ml, 500mg of calcium chloride as an intercalating agent was added, and the mixture was allowed to stand still for 2 days. And uniformly depositing the reacted graphene mixed solution on a polyethersulfone substrate film with the size of 10cm multiplied by 20cm in a knife coating mode, and then placing the film at 60 ℃ and with the humidity of 20% for 12 hours to prepare the lithium ion separation film of the large-size graphene oxide. The separation membrane layer spacing is 1.1nm and the thickness is 200nm. By adopting the method to treat 1L of brine solution with the magnesium-lithium ratio of 20, the magnesium-lithium ratio can be reduced to 2 by single filtration, and the magnesium-lithium ratio can be reduced to 0.1 after 3-5 times of filtration.
Example 2:
the lithium extraction film based on the large-size graphene oxide salt lake or brine comprises the following steps: graphene oxide (sheet thickness 1 nm) having an average size of 50 μm was prepared as 100ml of a graphene oxide solution having a concentration of 1mg/ml, and 500mg of lithium chloride as an intercalating agent was added and allowed to stand still for 2 days. And depositing the reacted graphene mixed solution on a polyethersulfone substrate film with the size of 10cm multiplied by 20cm in a negative pressure suction filtration mode, and then placing the suction filtered film at 50 ℃ and with the humidity of 30% for 12 hours to prepare the lithium ion separation film of the large-size graphene oxide. The separation membrane layer spacing is 1.0nm and the thickness is 100nm. By adopting the method to treat 1L of brine solution with the magnesium-lithium ratio of 50, the magnesium-lithium ratio can be reduced to 3.2,3-5 times by single filtration, and the magnesium-lithium ratio can be reduced to below 0.2 after filtration.
Example 3:
the lithium extraction film based on the large-size graphene oxide salt lake or brine comprises the following steps: graphene oxide with an average size of 15 μm (sheet thickness of 0.8 nm) was prepared as 100ml of graphene oxide solution with a concentration of 0.5mg/ml, and 300mg of intercalating agent 12-crown-4 ether was added and allowed to stand for 2 days for reaction. And uniformly depositing the reacted graphene mixed solution on a polyethersulfone substrate film with the size of 10cm multiplied by 20cm in a knife coating mode, and then placing the film at 60 ℃ and with the humidity of 20% for 12 hours to prepare the lithium ion separation film of the large-size graphene oxide. The separation membrane layer spacing is 0.4nm and the thickness is 20nm. By adopting the method to treat 1L of brine solution with the magnesium-lithium ratio of 20, the magnesium-lithium ratio can be reduced to 1.8,3-5 times by single filtration, and the magnesium-lithium ratio can be reduced to below 0.1 after filtration.
Example 4:
the lithium extraction film based on the large-size graphene oxide salt lake or brine comprises the following steps: graphene oxide (sheet thickness 0.9 nm) having an average size of 50 μm was prepared as 100ml of a graphene oxide solution having a concentration of 1mg/ml, and 500mg of lithium chloride as an intercalating agent was added and allowed to stand still for 2 days. And depositing the reacted graphene mixed solution on a polyethersulfone substrate film with the size of 10cm multiplied by 20cm by adopting a negative pressure suction filtration mode, and then placing the film at 50 ℃ and with the humidity of 30% for 12 hours to prepare the lithium ion separation film of the large-size graphene oxide. The separation membrane layer spacing was 0.9nm and the thickness was 50nm. By adopting the method to treat 1L of brine solution with the magnesium-lithium ratio of 50, the magnesium-lithium ratio can be reduced to 3.2,3-5 times by single filtration, and the magnesium-lithium ratio can be reduced to below 0.2 after filtration.
Example 5:
the lithium extraction film based on the large-size graphene oxide salt lake or brine comprises the following steps: graphene oxide with an average size of 5 μm (sheet thickness of 10 nm) was prepared as 100ml of graphene oxide solution with a concentration of 5mg/ml, 500mg of tetrabutylammonium chloride as an intercalating agent was added and allowed to stand still for 2 days. And uniformly depositing the reacted graphene mixed solution on a polyethersulfone substrate film with the size of 10cm multiplied by 20cm in a knife coating mode, and then placing the film at 100 ℃ and with the humidity of 30% for 24 hours to prepare the lithium ion separation film of the large-size graphene oxide. The separation membrane layer had a spacing of 5nm and a thickness of 50. Mu.m. By adopting the method to treat 1L of brine solution with the magnesium-lithium ratio of 50, the magnesium-lithium ratio can be reduced to 1.5,3-5 times by single filtration, and then the magnesium-lithium ratio can be reduced to 0.45.
Example 6:
the lithium extraction film based on the large-size graphene oxide salt lake or brine comprises the following steps: graphene oxide with an average size of 5 μm (the thickness of a sheet layer is 0.34 nm) is prepared into 100ml of graphene oxide solution with a concentration of 0.05mg/ml, and 5mg of intercalator 12-crown-4 ether is added and allowed to stand for reaction for 2 days. And depositing the reacted graphene mixed solution on a polyethersulfone substrate film by adopting a negative pressure suction filtration method, and then placing the film at 60 ℃ and a humidity of 20% for 12 hours to prepare the lithium ion separation film of the large-size graphene oxide. By adopting the method to treat 1L of brine solution with the magnesium-lithium ratio of 10, the magnesium-lithium ratio can be reduced to 1.8,3-5 by single filtration, and then the magnesium-lithium ratio can be reduced to 0.5.
Example 7:
the lithium extraction film based on the large-size graphene oxide salt lake or brine comprises the following steps: graphene oxide with an average size of 150 μm was prepared as 100ml of graphene oxide solution with a concentration of 5mg/ml, and 50mg of tetrabutylammonium chloride as an intercalating agent was added and allowed to stand for 2 days for reaction. And uniformly depositing the reacted graphene mixed solution on a nylon membrane with the size of 10cm multiplied by 20cm in a knife coating mode, and then placing the membrane at 60 ℃ and with the humidity of 20% for 12 hours to prepare the lithium ion separation membrane of the large-size graphene oxide. By adopting the method to treat 1L of brine solution with the magnesium-lithium ratio of 10, the magnesium-lithium ratio can be reduced to 0.9,3-5 times by single filtration, and then the magnesium-lithium ratio can be reduced to 0.2.
Example 8:
the lithium extraction film based on the large-size graphene oxide salt lake or brine comprises the following steps: graphene oxide with an average size of 150 μm is prepared into 100ml of graphene oxide solution with a concentration of 5mg/ml, 50mg of intercalation agent tetramethyl ammonium chloride is added, and the mixture is allowed to stand for reaction for 10min. And uniformly depositing the reacted graphene mixed solution on a mixed cellulose membrane with the size of 10cm multiplied by 20cm in a spin coating mode, and then placing the membrane at 20 ℃ and with the humidity of 10% for 15 hours to prepare the lithium ion separation membrane of the large-size graphene oxide.
Example 9:
the lithium extraction film based on the large-size graphene oxide salt lake or brine comprises the following steps: graphene oxide with an average size of 50 μm was prepared as 100ml of graphene oxide solution with a concentration of 0.05mg/ml, 500mg of intercalation agent dodecyltrimethylammonium chloride was added and allowed to stand for reaction for 5d. And depositing the reacted graphene mixed solution on an anodic aluminum oxide film with the size of 10cm multiplied by 20cm in a negative pressure suction filtration mode, and then placing the suction-filtered film at 120 ℃ and with the humidity of 30% for 20 hours to prepare the lithium ion separation film of the large-size graphene oxide.
Example 10:
the lithium extraction film based on the large-size graphene oxide salt lake or brine comprises the following steps: graphene oxide with an average size of 15 μm is prepared into 100ml of graphene oxide solution with a concentration of 0.5mg/ml, 300mg of intercalation agent tetradecyltrimethylammonium chloride is added, and the mixture is left to stand for reaction for 3d. And uniformly depositing the reacted graphene mixed solution on a polyethersulfone substrate film with the size of 10cm multiplied by 20cm in a knife coating mode, and then placing the film at the temperature of 100 ℃ and the humidity of 20% for 30min to prepare the lithium ion separation film of the large-size graphene oxide.
Example 11:
the lithium extraction film based on the large-size graphene oxide salt lake or brine comprises the following steps: graphene oxide with an average size of 50 μm is prepared into 100ml of graphene oxide solution with a concentration of 1mg/ml, 500mg of intercalator 15-crown-5 ether is added, and the mixture is left to stand for reaction for 1d. And depositing the reacted graphene mixed solution on a polyethersulfone substrate film with the size of 10cm multiplied by 20cm by adopting a negative pressure suction filtration mode, and then placing the film at the temperature of 30 ℃ and the humidity of 30% for 1d to prepare the lithium ion separation film of the large-size graphene oxide.
Example 12:
the lithium extraction film based on the large-size graphene oxide salt lake or brine comprises the following steps: graphene oxide with an average size of 50 μm is prepared into 100ml of graphene oxide solution with a concentration of 1mg/ml, 500mg of intercalator 18-crown-6 ether is added, and the mixture is left to stand for reaction for 5d. And depositing the reacted graphene mixed solution on a polyethersulfone substrate film with the size of 10cm multiplied by 20cm by adopting a negative pressure suction filtration mode, and then placing the film at the temperature of 40 ℃ and the humidity of 80% for 2d to prepare the lithium ion separation film of the large-size graphene oxide.
Comparative example 1:
graphene oxide having an average size of 2 μm was prepared as 100ml of a graphene oxide solution (sheet thickness of 1 nm) having a concentration of 1mg/ml, without adding an intercalating agent. And uniformly depositing the reacted graphene mixed solution on a polyethersulfone substrate film with the size of 10cm multiplied by 20cm in a knife coating mode, and then placing the film at 60 ℃ and with the humidity of 20% for 12 hours to prepare the lithium extraction film. The separation membrane layer spacing is 0.35nm and the thickness is 10nm. When 1L of brine solution with the magnesium-lithium ratio of 20 is treated, the magnesium-lithium ratio is reduced to 15 after about 1h of operation, but after 2h, the membrane is broken, and lithium cannot be extracted.
Comparative example 2:
graphene oxide (sheet thickness 15 nm) having an average size of 0.5 μm was prepared as 100ml of a graphene oxide solution having a concentration of 1mg/ml, and 500mg of calcium chloride as an intercalating agent was added and allowed to stand still for 2 days. And uniformly depositing the reacted graphene mixed solution on a polyethersulfone substrate film with the size of 10cm multiplied by 20cm by adopting a negative pressure suction filtration mode, and then placing the suction-filtered film at 60 ℃ and with the humidity of 20% for 12 hours to prepare the lithium extraction film. The separation film thickness was 8nm and the thickness was 80. Mu.m. When 1L of brine solution with a magnesium-lithium ratio of 20 is treated by the method, the membrane is broken, and lithium cannot be extracted.
Comparative example 3:
graphene oxide with an average size of 15 μm was prepared as 100ml of graphene oxide solution with a concentration of 20mg/ml, and 500mg of intercalating agent calcium chloride was added and allowed to stand for 2 days for reaction. And uniformly depositing the reacted graphene mixed solution on a polyethersulfone substrate film with the size of 10cm multiplied by 20cm in a knife coating mode, and then placing the film at 60 ℃ and with the humidity of 20% for 12 hours to prepare the lithium extraction film. The brine solution with the magnesium-lithium ratio of 20 is treated by adopting the method, the magnesium-lithium ratio is 18.5 after 1 day of operation, and the treatment capacity is lower.
Comparative example 4:
graphene oxide with an average size of 15 μm was prepared as 100ml of graphene oxide solution with a concentration of 2mg/ml, and an excessive amount of intercalating agent calcium chloride, 20g, was added and allowed to stand for 2 days for reaction. And uniformly depositing the reacted graphene mixed solution on a polyethersulfone substrate film with the size of 10cm multiplied by 20cm by adopting a negative pressure suction filtration mode, and then placing the suction-filtered film at 60 ℃ and with the humidity of 20% for 12 hours to prepare the lithium extraction film, wherein the surface of the film is very uneven. By adopting the method to treat 1L of brine solution with the magnesium-lithium ratio of 20, membrane breakage occurs after 1 h.
Comparative example 5:
graphene oxide with an average size of 0.8 μm was prepared as 100ml of graphene oxide solution with a concentration of 0.1mg/ml, and 500mg of intercalating agent lithium chloride was added and allowed to stand for 2 days for reaction. And uniformly depositing the reacted graphene mixed solution on a polyethersulfone substrate film with the size of 10cm multiplied by 20cm in a knife coating mode, and then placing the film at 220 ℃ and humidity of 20% for 20 hours to prepare the lithium extraction film of the large-size graphene oxide. By adopting the method to treat 1L of brine solution with the magnesium-lithium ratio of 20, the magnesium-lithium ratio can be reduced to 18 by single filtration, and can be reduced to 12 after 3-5 times of filtration, so that the effect is poor.
As shown in fig. 1, it can be seen from the optical microscope photograph of the large-size graphene oxide lithium ion separation membrane prepared in example 1 that the surface of the membrane is complete and a large number of wrinkles exist, which is beneficial for the infiltration of brine from the surface of the membrane.
As shown in fig. 2, it can be seen from a scanning electron microscope photograph of a cross section of the large-size graphene oxide lithium ion separation membrane prepared in example 2 that the prepared membrane is in a layer-by-layer stacking form, conforms to a face-to-face assembly structure of graphene sheets, and is beneficial to maintaining mechanical stability of the membrane and ensuring selective transmission of saline between layers.
By comparing the embodiment with the comparative example, the application utilizes the high mechanical strength of large-size graphene and the selective ion transmission channel between the sheets, and combines the adjustment of the interlayer spacing of the intercalation agent to finally realize the efficient lithium extraction from the brine. The application relates to a preparation method of a lithium ion separation membrane for salt lake water or salt solution system based on intercalation large-size graphene oxide, which comprises the working procedures of mixing large-size graphene with an intercalation agent, reacting intercalation, drying and film forming; the high-efficiency lithium extraction from salt lake water or salt solution system is finally realized by utilizing the high mechanical strength of large-size graphene and the selective ion transmission channel between the sheets and combining the adjustment of the intercalation agent on the membrane layer spacing.
The above is only for illustrating the technical idea of the present application, and the protection scope of the present application is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present application falls within the protection scope of the claims of the present application.
Claims (10)
1. The preparation method of the lithium ion separation membrane based on the intercalation large-size graphene oxide is characterized by comprising the following steps of:
mixing large-size graphene oxide sheets with average size of 5-150 mu m with deionized water to obtain a large-size graphene oxide solution;
and (3) blending the large-size graphene oxide solution with an intercalation agent, standing to obtain a mixed solution, depositing the mixed solution on a substrate film, and drying to obtain the lithium ion separation film.
2. The method for preparing the lithium ion separation membrane based on the intercalated large-size graphene oxide according to claim 1, wherein the concentration of the large-size graphene oxide solution is 0.05-5 mg/ml; the concentration ratio of the large-size graphene oxide solution to the intercalating agent is 1: (0.1-50); the thickness of the large-size graphene oxide sheet is 0.34-10 nm.
3. The preparation method of the lithium ion separation membrane based on the intercalated large-size graphene oxide, which is disclosed in claim 1, is characterized in that the intercalating agent is one or a combination of a chloride salt containing metal ions and a hydroxide containing metal ions, tetramethyl ammonium chloride, tetrabutyl ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, 12-crown-4 ether, 15-crown-5 ether and 18-crown-6 ether.
4. The method for preparing the lithium ion separation membrane based on the intercalated large-size graphene oxide according to claim 1, wherein the intercalating agent is located between or on the large-size graphene oxide sheets inside the lithium ion separation membrane.
5. The method for preparing the lithium ion separation membrane based on the intercalated large-size graphene oxide, which is disclosed in claim 1, is characterized in that the mode of depositing the mixed solution on the substrate membrane is any one of knife coating, spin coating and negative pressure suction filtration.
6. The method for preparing the lithium ion separation membrane based on the intercalated large-size graphene oxide according to claim 1, wherein the base membrane is any one of a polyethersulfone membrane, a nylon membrane, a mixed cellulose membrane and an anodic aluminum oxide membrane.
7. The method for preparing the lithium ion separation membrane based on the intercalated large-size graphene oxide, which is disclosed in claim 1, is characterized in that the temperature of the drying treatment is 20-120 ℃, the humidity of the drying treatment is 10-80%, and the time of the drying treatment is 30 min-2 d.
8. A lithium ion separation membrane prepared by the method for preparing an intercalation large-size graphene oxide-based lithium ion separation membrane according to any one of claims 1 to 7.
9. The lithium ion separation membrane based on intercalated large-sized graphene oxide of claim 8, wherein the interlayer spacing of the lithium ion separation membrane is 0.4-5 nm; the thickness of the lithium ion separation membrane is 20 nm-50 mu m.
10. The lithium ion separation membrane based on intercalated large-size graphene oxide according to claim 8, wherein the lithium ion separation membrane is applied to selective filtration separation of lithium ions in salt lake water or salt solution systems.
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