CN114100570A - Preparation method and application of lithium ion selective adsorption membrane - Google Patents

Preparation method and application of lithium ion selective adsorption membrane Download PDF

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CN114100570A
CN114100570A CN202010861793.1A CN202010861793A CN114100570A CN 114100570 A CN114100570 A CN 114100570A CN 202010861793 A CN202010861793 A CN 202010861793A CN 114100570 A CN114100570 A CN 114100570A
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graphene oxide
oxide film
lithium ion
selective adsorption
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CN114100570B (en
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方海平
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East China University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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

Abstract

The invention discloses a preparation method of a lithium ion selective adsorption film, which comprises the following steps: step one, preparing a graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by an oxidation stripping graphite method, wherein the suspended graphene sheet layer is about 0.5-1.0 nm in thickness of a monoatomic layer, and the sheet layer size diameter is 1-50 mu m; step two, preparing a graphene oxide film: preparing the graphene oxide suspension prepared in the first step into a graphene oxide film by a dropping coating method, a suction filtration method, a spin coating method and the like; thirdly, thermal reduction: and (3) carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film. The preparation method is simple and easy to operate, and the prepared film has stable properties and is not easy to break and has the function of selectively adsorbing lithium ions.

Description

Preparation method and application of lithium ion selective adsorption membrane
Technical Field
The invention belongs to the technical field of a preparation method of a lithium ion selective adsorption film and a process for extracting lithium from brine, and particularly relates to a preparation method of a lithium ion selective adsorption film capable of selectively adsorbing lithium ions in brine with a high magnesium-lithium ratio and application thereof.
Background
Lithium is known as "Energy metal" and "metal promoting the world", and is widely Applied to lithium ion batteries (Advanced Functional Materials 2017, 27; Nat Mater 2017,16,572 + 579; Nat commu 2019,10,1081), storage devices (Science 2011,334,928 + 935; Nat Mater 2011,11,19-29), alloy technology (Nat commu 2019,10,3428), glass (Sci Rep 2019,9,16607) and ceramics (Journal of Power Sources 2013,228,250 + 255), and the application field of lithium is continuously expanded at present, and the demand of lithium is continuously increased all over the world (Applied Energy 2013,110,252 + 266).
Lithium is mainly from solid lithium-containing ores and brine lithium resources, almost 60 percent of lithium exists in salt lake brine lithium resources all over the world, and the salt lake is considered as a main source of lithium. However, most of Li in salt lake brine+Has low concentration and coexists with a large amount of alkali metal ions and alkaline earth metal ions due to their close chemical properties, especially the ionic radius and Li+Closest Mg2+Its content is very high, and magnesium and lithium in salt lake are high (Hydrometallurgy 2018,176,73-77), which makes it very difficult to separate and extract lithium from it.
There are many methods for extracting lithium from salt lake brine, including precipitation (Green Chemistry 2018,20,3121-3133), salting-out (Journal of Membrane Science 2016,505,167-173), solvent extraction (Hydrometallurgy 2017,171,27-32), and ion exchange adsorption (Hydrometallurgy 2010,102, 37-42; Applied Surface Science 2018,427, 931-941). Wherein, the product obtained by the precipitation method has low purity and is not suitable for salt lakes with high magnesium content; the salting-out method has low total recovery rate and needs to be operated under a closed condition; solution extraction requires an extractant, an extraction base and corrosion-resistant materials, and is polluting. The adsorption method has simple process and high recovery rate, has certain advantages in terms of economy and environmental protection compared with other methods, and is particularly suitable for separating and extracting lithium from salt lake brine with high magnesium-lithium ratio. The adsorption method can be classified into an organic ion adsorption method and an inorganic ion adsorption method according to the kind of the adsorbent, and the organic ion adsorption method generally utilizes an organic ion adsorbent to adsorb Li by means of coulomb force+(ii) a The inorganic ion adsorption method utilizes inorganic ion adsorptionAdjuvant pair Li+Has the characteristics of higher selectivity and specific memory effect, and realizes the method for selectively extracting lithium from the dilute Li + solution. However, most of the adsorbents with good adsorption performance are powder type adsorbents, the particle size is small, the fluidity and the permeability are poor, the dissolution loss rate is high, the granulation is difficult, the large-scale industrialization is difficult to realize, and the actual lithium adsorption capacity of most of the adsorbents has some differences from the theoretical maximum adsorption capacity, so that the problem to be solved in the lithium extraction by the adsorption method is urgent.
Disclosure of Invention
The invention aims to provide a preparation method of a lithium ion selective adsorption film, the prepared lithium ion selective adsorption film solves the technical problems that a lithium ion adsorbent in the prior art is difficult to granulate, high in dissolution loss rate, difficult to realize large-scale industrialization and the like, a reduced graphene oxide film is obtained by carrying out thermal reduction treatment on a graphene oxide film, the interlayer spacing of the reduced graphene oxide film is effectively controlled, and the interlayer spacing of the reduced graphene oxide film is obtained by carrying out thermal treatment at 140-180 DEG C
Figure BDA0002648395520000021
The graphene oxide film obtained by heat treatment at 140 ℃ has the best selective adsorption effect on lithium ions, so that lithium can be efficiently and selectively adsorbed and separated from salt lake brine with a high magnesium-lithium ratio.
The second purpose of the invention is to provide the application of the lithium ion selective adsorption membrane prepared by the method as a lithium ion adsorbent.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a preparation method of a lithium ion selective adsorption membrane, which comprises the following steps:
step one, preparing a graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by an oxidation stripping graphite method, wherein the suspended graphene sheet layer is about 0.5-1.0 nm in thickness of a monoatomic layer, and the sheet layer size diameter is 1-50 mu m;
step two, preparing a graphene oxide film: preparing the graphene oxide suspension prepared in the first step into a graphene oxide film by a dropping coating method, a suction filtration method, a spin coating method and the like;
thirdly, thermal reduction: and (3) carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film.
The graphene oxide suspension is prepared by a Hummers method, but is not limited to the oxidation exfoliation method.
The concentration of the graphene oxide suspension is 1-6 mg/mL, and preferably 5 mg/mL.
The graphene oxide film is a graphene oxide film conventionally used in the art, and may be a stand-alone film or a support film of graphene oxide.
The graphene oxide film has a thickness of about 30 μm.
The dropping method is a dropping method which is conventional in the field, and the specific method comprises the following steps: and dripping the graphene oxide suspension on the smooth paper surface, and drying to obtain the graphene oxide independent film.
The suction filtration method is a conventional suction filtration method in the field, and comprises the following steps: carrying out suction filtration on the graphene oxide suspension, and drying the filter membrane to obtain a support membrane of the graphene oxide; wherein the suction filtration is filter membrane suction filtration; the filter is a filter conventionally used in the art, preferably an aqueous filter, having a pore size of 0.22 μm and a diameter of 38 mm.
The spin coating method is a conventional spin coating method in the field, and the specific method comprises the following steps: and (3) coating the graphene oxide suspension on a substrate, rotating the substrate to uniformly disperse the solution on the surface of the substrate, and drying the substrate to obtain the graphene oxide independent film.
The drying operations and conditions are those conventional in the art, and the drying process is: drying for 1-24 h (preferably 60 ℃ C., and preferably 12h) at 50-70 ℃, repeatedly leaching with deionized water, soaking in deionized water for 0.1-1 h (preferably 0.5h), taking out, and drying for 1-24 h (preferably 60 ℃ C., and preferably 6h) at 50-70 ℃.
The temperature of the high-temperature thermal reduction treatment is 100-180 ℃, preferably 140-180 ℃, and more preferably 140 ℃; the time is 1-24 h, preferably 1-4 h.
The interlayer spacing of the lithium ion selective adsorption film is as follows: the interlayer spacing of the reduced graphene oxide film obtained by heat treatment at 140 ℃ and 180 ℃ is
Figure BDA0002648395520000031
The second aspect of the invention provides an application of the lithium ion selective adsorption membrane prepared by the method as a lithium ion adsorbent.
The third aspect of the invention provides a lithium ion selective adsorption membrane prepared by the method as a lithium ion adsorbent for selectively adsorbing lithium ions in salt lake brine.
After the salt lake brine is evaporated and concentrated, the mass ratio of magnesium ions to lithium ions is 1000: 1-0.5: 1, and preferably 500: 1.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the lithium ion selective adsorption membrane provided by the invention is a reduced graphene oxide membrane, on one hand, a carbon nano material has a higher specific surface area and a large lithium adsorption capacity, and on the other hand, the lithium ion selective adsorption membrane has a good lithium ion selective adsorption effect in salt lake brine with a high magnesium-lithium ratio, and in addition, the reduced graphene oxide membrane has stable properties and can be recycled for multiple times.
The lithium ion selective adsorption film prepared by the method is a reduced graphene oxide film prepared by a thermal reduction method, effectively controls the interlayer spacing of the reduced graphene oxide, realizes high-efficiency selective adsorption of lithium ions in a mixed salt solution based on the size effect principle, and uses the prepared reduced graphene oxide film to perform six-cycle experiments to obtain Mg in a magnesium-lithium ion mixed solution2+/Li+The mass ratio is initially 500:1, final desorption of Mg of the resulting mixed solution2+/Li+The mass ratio is reduced to0.7:1, the reduced graphene oxide film can effectively perform selective adsorption and desorption treatment on lithium ions in salt lake brine with a high magnesium-lithium ratio. The preparation method is simple and easy to operate, and the prepared film has stable properties and is not easy to break and has the function of selectively adsorbing lithium ions. The invention also provides a process for extracting lithium from salt lake brine based on the reduced graphene oxide membrane, and the process has a good application prospect in the fields of batteries, supercapacitors, automobiles, aerospace, metallurgy and the like.
Drawings
Fig. 1 is a schematic physical photograph of a reduced graphene oxide film prepared by the method of the present invention.
FIG. 2 is a schematic representation of the surface topography of a scanning electron microscope characterization of reduced graphene oxide films prepared using the method of the present invention.
FIG. 3 is a schematic representation of a scanning electron microscopy characterization of a reduced graphene oxide film prepared using the method of the present invention.
Figure 4 is a graph of XRD interlayer spacing data for the dried reduced graphene oxide films of examples 1-9 of the present invention.
FIG. 5 shows the reduced graphene oxide film immersed in Mg in examples 1 to 9 of the present invention2+、Li+XRD interlamellar distance data graph of the wet reduced graphene oxide film after 0.5h in the mixed solution of 1 mol/L.
Fig. 6 is a Raman test spectrum of the reduced graphene oxide film in examples 1 to 9 of the present invention.
Fig. 7 is a graph showing the change in the ratio of the D peak intensity to the G peak intensity in the Raman test spectra of the reduced graphene oxide films according to examples 1 to 9 of the present invention.
FIG. 8 is Li+、Mg2+Single ion solution adsorption capacity graph.
FIG. 9 shows the reduced graphene oxide film soaked in Li in examples 1 to 9 of the present invention+、Mg2+The molar ratio is 1:1, the change of selective adsorption effect.
FIG. 10 shows the reduced graphene oxide film soaked in Li in examples 1 to 9 of the present invention+、Mg2+Li in mixed solution+Change of adsorption capacityAnd (6) forming a graph.
FIG. 11 shows the reduced graphene oxide film soaked in Li in examples 1 to 9 of the present invention+、Mg2+Mg in the mixed solution2+Graph of change in adsorption capacity.
Fig. 12 is a graph showing the results of a cycle lithium extraction experiment of the reduced graphene oxide film for a high mg/li ratio solution in example 5 of the present invention.
FIG. 13 is a graph showing the time-dependent change in properties of a reduced graphene oxide film in example 5 of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
The preparation method of the lithium ion selective adsorption membrane comprises the following steps:
step one, preparing a graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by an oxidation stripping graphite method (J.Am.chem.Soc.1958,80,1339), wherein the suspended graphene sheet layer is about 0.5-1.0 nm in thickness and 1-50 mu m in sheet size diameter; graphite powder is oxidized and stripped by using a Hummers method to obtain a graphene oxide suspension, wherein the concentration of the graphene oxide suspension is 5 mg/mL.
Step two, preparing a graphene oxide film: preparing the graphene oxide suspension prepared in the first step by a dropping coating method to obtain an independent film of graphene oxide, which comprises the following specific steps:
dropping 1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step on a smooth paper sheet, drying the smooth paper sheet in an oven at 60 ℃ for 12h, taking down an independent graphene oxide film, repeatedly leaching the independent graphene oxide film with deionized water, soaking the independent graphene oxide film in a large amount of deionized water for half an hour, taking out the independent graphene oxide film, drying the independent graphene oxide film in the oven at 60 ℃ for 6h, and putting the independent graphene oxide film into a drying dish for use, wherein the thickness of the obtained graphene oxide film is about 30 micrometers.
Thirdly, thermal reduction: oxidizing the second stepCarrying out high-temperature thermal reduction treatment on the graphene film for 1-4h by an oven at the temperature of 100 ℃ to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film named rGO-100, and detecting the interlayer spacing of the dried reduced graphene oxide film by XRD (X-ray diffraction)
Figure BDA0002648395520000053
Immersing the dried reduced graphene oxide film in the mixed Mg2+、Li+Obtaining a wet reduced graphene oxide film in the ionic solution, and detecting the interlayer spacing of the wet reduced graphene oxide film by XRD (X-ray diffraction)
Figure BDA0002648395520000054
Example 2
The preparation method of the lithium ion selective adsorption membrane comprises the following steps:
step one, preparing a graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by an oxidation stripping graphite method, wherein the suspended graphene sheet layer is about 0.5-1.0 nm in thickness of a monoatomic layer, and the sheet layer size diameter is 1-50 mu m; graphite powder is oxidized and stripped by using a Hummers method to obtain a graphene oxide suspension, wherein the concentration of the graphene oxide suspension is 5 mg/mL.
Step two, preparing a graphene oxide film: preparing the graphene oxide suspension prepared in the first step by a dropping coating method to obtain an independent film of graphene oxide, which comprises the following specific steps:
dropping 1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step on a smooth paper sheet, drying the smooth paper sheet in an oven at 60 ℃ for 12h, taking down an independent graphene oxide film, repeatedly leaching the independent graphene oxide film with deionized water, soaking the independent graphene oxide film in a large amount of deionized water for half an hour, taking out the independent graphene oxide film, drying the independent graphene oxide film in the oven at 60 ℃ for 6h, and putting the independent graphene oxide film into a drying dish for use, wherein the thickness of the obtained graphene oxide film is about 30 micrometers.
Thirdly, thermal reduction: subjecting the graphene oxide film prepared in the second step to high-temperature thermal reduction treatment for 1-4h in an oven at the temperature of 110 ℃ to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film, namedFor rGO-110, the XRD detects the interlayer spacing of the dried reduced graphene oxide film, namely
Figure BDA0002648395520000051
Immersing the dried reduced graphene oxide film in the mixed Mg2+、Li+Obtaining a wet reduced graphene oxide film in the ionic solution, and detecting the interlayer spacing of the wet reduced graphene oxide film by XRD (X-ray diffraction)
Figure BDA0002648395520000052
Example 3
The preparation method of the lithium ion selective adsorption membrane comprises the following steps:
step one, preparing a graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by an oxidation stripping graphite method, wherein the suspended graphene sheet layer is about 0.5-1.0 nm in thickness of a monoatomic layer, and the sheet layer size diameter is 1-50 mu m; graphite powder is oxidized and stripped by using a Hummers method to obtain a graphene oxide suspension, wherein the concentration of the graphene oxide suspension is 5 mg/mL.
Step two, preparing a graphene oxide film: preparing the graphene oxide suspension prepared in the first step by a dropping coating method to obtain an independent film of graphene oxide, which comprises the following specific steps:
dropping 1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step on a smooth paper sheet, drying the smooth paper sheet in an oven at 60 ℃ for 12h, taking down an independent graphene oxide film, repeatedly leaching the independent graphene oxide film with deionized water, soaking the independent graphene oxide film in a large amount of deionized water for half an hour, taking out the independent graphene oxide film, drying the independent graphene oxide film in the oven at 60 ℃ for 6h, and putting the independent graphene oxide film into a drying dish for use, wherein the thickness of the obtained graphene oxide film is about 30 micrometers.
Thirdly, thermal reduction: carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step for 1-4h by using an oven at the temperature of 120 ℃ to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film named rGO-120, and detecting the interlayer spacing of the dried reduced graphene oxide film by XRD (X-ray diffraction), wherein
Figure BDA0002648395520000061
Immersing the dried reduced graphene oxide film in the mixed Mg2+、Li+Obtaining a wet reduced graphene oxide film in the ionic solution, and detecting the interlayer spacing of the wet reduced graphene oxide film by XRD (X-ray diffraction)
Figure BDA0002648395520000062
Example 4
The preparation method of the lithium ion selective adsorption membrane comprises the following steps:
step one, preparing a graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by an oxidation stripping graphite method, wherein the suspended graphene sheet layer is about 0.5-1.0 nm in thickness of a monoatomic layer, and the sheet layer size diameter is 1-50 mu m; graphite powder is oxidized and stripped by using a Hummers method to obtain a graphene oxide suspension, wherein the concentration of the graphene oxide suspension is 5 mg/mL.
Step two, preparing a graphene oxide film: preparing the graphene oxide suspension prepared in the first step by a dropping coating method to obtain an independent film of graphene oxide, which comprises the following specific steps:
dropping 1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step on a smooth paper sheet, drying the smooth paper sheet in an oven at 60 ℃ for 12h, taking down an independent graphene oxide film, repeatedly leaching the independent graphene oxide film with deionized water, soaking the independent graphene oxide film in a large amount of deionized water for half an hour, taking out the independent graphene oxide film, drying the independent graphene oxide film in the oven at 60 ℃ for 6h, and putting the independent graphene oxide film into a drying dish for use, wherein the thickness of the obtained graphene oxide film is about 30 micrometers.
Thirdly, thermal reduction: subjecting the graphene oxide film prepared in the second step to high-temperature thermal reduction treatment for 1-4h in an oven at the temperature of 130 ℃ to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film named rGO-130, and detecting the interlayer spacing of the dried reduced graphene oxide film by XRD (X-ray diffraction), wherein the interlayer spacing is
Figure BDA0002648395520000071
Immersing the dried reduced graphene oxide film in the mixed Mg2+、Li+Ionic solutionsObtaining a wet reduced graphene oxide film, and detecting the interlayer spacing of the wet reduced graphene oxide film by XRD (X-ray diffraction)
Figure BDA0002648395520000072
Example 5
The preparation method of the lithium ion selective adsorption membrane comprises the following steps:
step one, preparing a graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by an oxidation stripping graphite method, wherein the suspended graphene sheet layer is about 0.5-1.0 nm in thickness of a monoatomic layer, and the sheet layer size diameter is 1-50 mu m; graphite powder is oxidized and stripped by using a Hummers method to obtain a graphene oxide suspension, wherein the concentration of the graphene oxide suspension is 5 mg/mL.
Step two, preparing a graphene oxide film: preparing the graphene oxide suspension prepared in the first step by a dropping coating method to obtain an independent film of graphene oxide, which comprises the following specific steps:
dropping 1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step on a smooth paper sheet, drying the smooth paper sheet in an oven at 60 ℃ for 12h, taking down an independent graphene oxide film, repeatedly leaching the independent graphene oxide film with deionized water, soaking the independent graphene oxide film in a large amount of deionized water for half an hour, taking out the independent graphene oxide film, drying the independent graphene oxide film in the oven at 60 ℃ for 6h, and putting the independent graphene oxide film into a drying dish for use, wherein the thickness of the obtained graphene oxide film is about 30 micrometers.
Thirdly, thermal reduction: carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step for 1-4h by using an oven at the temperature of 140 ℃ to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film named rGO-140, and detecting the interlayer spacing of the dried reduced graphene oxide film by XRD (X-ray diffraction), wherein
Figure BDA0002648395520000073
Immersing the dried reduced graphene oxide film in the mixed Mg2+、Li+Obtaining a wet reduced graphene oxide film in the ionic solution, and detecting the interlayer spacing of the wet reduced graphene oxide film by XRD (X-ray diffraction)
Figure BDA0002648395520000074
Example 6
The preparation method of the lithium ion selective adsorption membrane comprises the following steps:
step one, preparing a graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by an oxidation stripping graphite method, wherein the suspended graphene sheet layer is about 0.5-1.0 nm in thickness of a monoatomic layer, and the sheet layer size diameter is 1-50 mu m; graphite powder is oxidized and stripped by using a Hummers method to obtain a graphene oxide suspension, wherein the concentration of the graphene oxide suspension is 5 mg/mL.
Step two, preparing a graphene oxide film: preparing the graphene oxide suspension prepared in the first step by a dropping coating method to obtain an independent film of graphene oxide, which comprises the following specific steps:
dropping 1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step on a smooth paper sheet, drying the smooth paper sheet in an oven at 60 ℃ for 12h, taking down an independent graphene oxide film, repeatedly leaching the independent graphene oxide film with deionized water, soaking the independent graphene oxide film in a large amount of deionized water for half an hour, taking out the independent graphene oxide film, drying the independent graphene oxide film in the oven at 60 ℃ for 6h, and putting the independent graphene oxide film into a drying dish for use, wherein the thickness of the obtained graphene oxide film is about 30 micrometers.
Thirdly, thermal reduction: carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step for 1-4h by using an oven at the temperature of 150 ℃ to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film named rGO-150, and detecting the interlayer spacing of the dried reduced graphene oxide film by XRD (X-ray diffraction), wherein
Figure BDA0002648395520000081
Immersing the dried reduced graphene oxide film in the mixed Mg2+、Li+Obtaining a wet reduced graphene oxide film in the ionic solution, and detecting the interlayer spacing of the wet reduced graphene oxide film by XRD (X-ray diffraction)
Figure BDA0002648395520000082
Example 7
The preparation method of the lithium ion selective adsorption membrane comprises the following steps:
step one, preparing a graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by an oxidation stripping graphite method, wherein the suspended graphene sheet layer is about 0.5-1.0 nm in thickness of a monoatomic layer, and the sheet layer size diameter is 1-50 mu m; graphite powder is oxidized and stripped by using a Hummers method to obtain a graphene oxide suspension, wherein the concentration of the graphene oxide suspension is 5 mg/mL.
Step two, preparing a graphene oxide film: preparing the graphene oxide suspension prepared in the first step by a dropping coating method to obtain an independent film of graphene oxide, which comprises the following specific steps:
dropping 1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step on a smooth paper sheet, drying the smooth paper sheet in an oven at 60 ℃ for 12h, taking down an independent graphene oxide film, repeatedly leaching the independent graphene oxide film with deionized water, soaking the independent graphene oxide film in a large amount of deionized water for half an hour, taking out the independent graphene oxide film, drying the independent graphene oxide film in the oven at 60 ℃ for 6h, and putting the independent graphene oxide film into a drying dish for use, wherein the thickness of the obtained graphene oxide film is about 30 micrometers.
Thirdly, thermal reduction: carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step for 1-4h by using an oven at the temperature of 160 ℃ to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film named rGO-160, and detecting the interlayer spacing of the dried reduced graphene oxide film by XRD (X-ray diffraction), wherein
Figure BDA0002648395520000083
Immersing the dried reduced graphene oxide film in the mixed Mg2+、Li+Obtaining a wet reduced graphene oxide film in the ionic solution, and detecting the interlayer spacing of the wet reduced graphene oxide film by XRD (X-ray diffraction)
Figure BDA0002648395520000084
Example 8
The preparation method of the lithium ion selective adsorption membrane comprises the following steps:
step one, preparing a graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by an oxidation stripping graphite method, wherein the suspended graphene sheet layer is about 0.5-1.0 nm in thickness of a monoatomic layer, and the sheet layer size diameter is 1-50 mu m; graphite powder is oxidized and stripped by using a Hummers method to obtain a graphene oxide suspension, wherein the concentration of the graphene oxide suspension is 5 mg/mL.
Step two, preparing a graphene oxide film: preparing the graphene oxide suspension prepared in the first step by a dropping coating method to obtain an independent film of graphene oxide, which comprises the following specific steps:
dropping 1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step on a smooth paper sheet, drying the smooth paper sheet in an oven at 60 ℃ for 12h, taking down an independent graphene oxide film, repeatedly leaching the independent graphene oxide film with deionized water, soaking the independent graphene oxide film in a large amount of deionized water for half an hour, taking out the independent graphene oxide film, drying the independent graphene oxide film in the oven at 60 ℃ for 6h, and putting the independent graphene oxide film into a drying dish for use, wherein the thickness of the obtained graphene oxide film is about 30 micrometers.
Thirdly, thermal reduction: carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step for 1-4h by using an oven at the temperature of 170 ℃ to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film named rGO-170, and detecting the interlayer spacing of the dried reduced graphene oxide film by XRD (X-ray diffraction), wherein
Figure BDA0002648395520000091
Immersing the dried reduced graphene oxide film in the mixed Mg2+、Li+Obtaining a wet reduced graphene oxide film in the ionic solution, and detecting the interlayer spacing of the wet reduced graphene oxide film by XRD (X-ray diffraction)
Figure BDA0002648395520000092
Example 9
The preparation method of the lithium ion selective adsorption membrane comprises the following steps:
step one, preparing a graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by an oxidation stripping graphite method, wherein the suspended graphene sheet layer is about 0.5-1.0 nm in thickness of a monoatomic layer, and the sheet layer size diameter is 1-50 mu m; graphite powder is oxidized and stripped by using a Hummers method to obtain a graphene oxide suspension, wherein the concentration of the graphene oxide suspension is 5 mg/mL.
Step two, preparing a graphene oxide film: preparing the graphene oxide suspension prepared in the first step by a dropping coating method to obtain an independent film of graphene oxide, which comprises the following specific steps:
dropping 1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step on a smooth paper sheet, drying the smooth paper sheet in an oven at 60 ℃ for 12h, taking down an independent graphene oxide film, repeatedly leaching the independent graphene oxide film with deionized water, soaking the independent graphene oxide film in a large amount of deionized water for half an hour, taking out the independent graphene oxide film, drying the independent graphene oxide film in the oven at 60 ℃ for 6h, and putting the independent graphene oxide film into a drying dish for use, wherein the thickness of the obtained graphene oxide film is about 30 micrometers.
Thirdly, thermal reduction: carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step for 1-4h by using an oven at the temperature of 180 ℃ to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film named rGO-180, and detecting the interlayer spacing of the dried reduced graphene oxide film by XRD (X-ray diffraction), wherein
Figure BDA0002648395520000093
Immersing the dried reduced graphene oxide film in the mixed Mg2+、Li+Obtaining a wet reduced graphene oxide film in the ionic solution, and detecting the interlayer spacing of the wet reduced graphene oxide film by XRD (X-ray diffraction)
Figure BDA0002648395520000101
The characterization test of the reduced graphene oxide film prepared by the embodiment of the invention comprises the following steps:
1. SEM, XRD and Raman characterization
The reduced graphene oxide film prepared in example 5 was characterized by SEM using Hitachi, S-4800 for SEM examination.
The reduced graphene oxide films prepared in examples 1-9 were characterized by XRD using a D8AA 25X-ray diffractometer (Bruker, Germany) with a test range of 5-30 ° and a step size of 0.15 °.
The reduced graphene oxide films prepared in examples 1-9 were characterized by Raman, and HR 800 was used for Raman detection.
The physical photograph appearance diagram of the reduced graphene oxide film is shown in fig. 1, and fig. 1 is a physical photograph schematic diagram of the reduced graphene oxide film prepared by the method. The SEM micrographs are shown in fig. 2 and 3, fig. 2 is a schematic surface morphology representation of a scanning electron microscope of the reduced graphene oxide film prepared by the method of the present invention, and fig. 3 is a schematic cross-sectional morphology representation of a scanning electron microscope of the reduced graphene oxide film prepared by the method of the present invention. The loose and porous structure of the reduced graphene oxide can be seen from the figure.
XRD characterization patterns are shown in fig. 4 and 5, and fig. 4 is a graph of XRD interlayer spacing data for the reduced graphene oxide films dried in examples 1-9 of the present invention. FIG. 5 shows the reduced graphene oxide film immersed in Mg in examples 1 to 9 of the present invention2+、Li+XRD interlamellar distance data graph of the wet reduced graphene oxide film after 0.5h in the mixed solution of 1 mol/L. As can be seen from the figure, the interlayer spacing of the reduced graphene oxide film after the high-temperature heat treatment at 140 ℃ and 180 ℃ is obviously reduced
Figure BDA0002648395520000102
The Raman characterization results are shown in fig. 6 and 7, and fig. 6 is a Raman test spectrum of the reduced graphene oxide film in examples 1 to 9 of the present invention. Fig. 7 is a graph showing the change in the ratio of the D peak intensity to the G peak intensity in the Raman test spectra of the reduced graphene oxide films according to examples 1 to 9 of the present invention. As can be seen from the figure, the D peak (. about.1352 cm)-1) Is a defect peak, the G peak (. about.1570 cm)-1) The ratio of the D peak to G peak intensity (ID/IG) of the rGO film increases with the increase of the reduction temperature, and the number of defects in the reduced graphene oxide film increases.
2. Selective adsorption film of lithium ion for Mg separately2+、Li+Adsorption experiment of solution
10mg of the lithium ion-selective adsorbent membrane prepared in example 5 was placed at a temperature of 20 deg.C30mL of initial Li+Soaking LiCl solution with the concentration of 1mol/L for 0.5h, taking out the lithium ion selective adsorption film, centrifuging to remove the solution on the surface of the film, then placing the lithium ion selective adsorption film in 30mL of dilute hydrochloric acid solution with the concentration of 0.2mol/L for desorption for 0.5h, and measuring Li in the desorption solution by using an inductively coupled plasma emission spectrometer after desorption+And (4) calculating the adsorption quantity. The calculation formula is as follows
QLi＝CLi×V/m
Wherein Q isLiIs Li+The adsorption capacity of (a); cLiIs Li desorbed from the solution+Concentration; v is the volume of desorption solution; and m is the mass of the adsorption film.
10Mg of the lithium ion selective adsorption membrane prepared in example 5 was placed in 30mL of the original Mg at a temperature of 20 deg.C2+MgCl at a concentration of 1mol/L2Soaking the solution for 0.5h, taking out the lithium ion selective adsorption film, centrifuging to remove the solution on the surface of the film, then placing the lithium ion selective adsorption film in 30mL of 0.2mol/L dilute hydrochloric acid solution for desorption for 0.5h, and measuring Mg in the desorption solution by using an inductively coupled plasma emission spectrometer after desorption2+And (4) calculating the adsorption quantity. The calculation formula is as follows
QMg＝CMg×V/m
Wherein Q isMgIs Mg2+The adsorption capacity of (a); cMgIs Mg of the desorption solution2+Concentration; v is the volume of desorption solution; and m is the mass of the adsorption film.
Wherein the amount of adsorption is shown in FIG. 8, and FIG. 8 shows Li+、Mg2+Single ion solution adsorption capacity graph. As can be seen from the figure, when the ion concentrations of the initial solutions are all 1mol/L, the lithium ion selective adsorption film is used for Li+An adsorbed amount of 10.4Mg/g (1.51mmol/g) for Mg2+The adsorbed amount was 38.4mg/g (1.58 mmol/g). The experimental result shows that in the single-ion solution, the lithium ion selective adsorption film is used for Li+And Mg2+Almost the molar amount of adsorption of (a).
3、Mg2+/Li+Selective adsorption test
In practical industrial processes, there is a need to selectively extract Li from large amounts of mixed ion solutions+. Therefore, the selective adsorption performance is an important index for examining the lithium ion selective adsorption film.
Under the condition of 20 ℃ temperature, the preparation contains Li+And Mg2+Mixed solution of (2), Li+And Mg2+The initial concentration of (a) was 1mol/L, 10mg of the lithium ion selective adsorption membrane prepared in examples 1 to 9 was placed in 30mL of a mixed solution, soaked for 0.5h, then the lithium ion selective adsorption membrane was taken out and centrifuged to remove the membrane surface solution, then the lithium ion selective adsorption membrane was placed in 30mL of a 0.2mol/L dilute hydrochloric acid solution for desorption for 0.5h, and after desorption was completed, Li in the desorption solution was measured using an inductively coupled plasma emission spectrometer+And Mg2+And (4) calculating the selective adsorption performance and the adsorption quantity.
The adsorption performance is calculated as follows
K0＝1
Ke＝CMg/CLi
Wherein, K0Is Mg in the initial mixed solution2+/Li+The molar ratio is 1; ke is desorption of Mg in solution2+/Li+A molar ratio; cMgIs Mg of the desorption solution2+Concentration, CLiIs Li desorbed from the solution+Concentration;
as shown in FIG. 9, FIG. 9 shows the reduced graphene oxide film soaked in Li in examples 1 to 9 of the present invention+、Mg2+The molar ratio is 1:1, the change of selective adsorption effect. The reduced graphene oxide films of examples 1-9 were immersed in Mg2+/Li+The molar ratio is 1:1, soaking the reduced graphene oxide film in a dilute hydrochloric acid solution for desorption after adsorption is finished, and measuring Li in the desorption solution by using an inductively coupled plasma emission spectrometer+And Mg2+Concentration and Mg2+/Li+The molar ratio. It can be seen from the figure that the temperature of the heat treatment is changed fromMg when the temperature is increased to 140 ℃ at 100 DEG C2+/Li+The molar ratio is continuously reduced, which indicates that the reduced graphene oxide film is opposite to Li+The selective adsorption effect of (A) is continuously increased; mg as the heat treatment temperature increases from 140 ℃ to 180 ℃2+/Li+The molar ratio was slightly increased, indicating that the reduced graphene oxide film was paired with Li+The selective adsorption effect is reduced. The experimental result shows that the reduced graphene oxide film obtained by heat treatment at 140 ℃ has the best selective adsorption effect on lithium ions.
The adsorption amount is calculated as follows
QLi＝CLi×V/m
QMg＝CMg×V/m
Wherein Q isLiIs Li+The adsorption capacity of (a); cLiIs Li desorbed from the solution+Concentration; qMgIs Mg2+The adsorption capacity of (a); cMgIs Mg of the desorption solution2+Concentration; v is the volume of desorption solution; and m is the mass of the adsorption film.
Wherein the adsorption amounts are shown in FIG. 10 and FIG. 11, and FIG. 10 shows that the reduced graphene oxide films were soaked in Li in examples 1 to 9 of the present invention+、Mg2+Li in mixed solution+FIG. 11 is a graph showing changes in adsorption capacity of reduced graphene oxide films immersed in Li in examples 1 to 9 of the present invention+、Mg2+Mg in the mixed solution2+Graph of change in adsorption capacity. It can be seen from the figure that with the continuous increase of the heat treatment temperature, the adsorption capacity of the reduced graphene oxide film is also continuously changed, and the change trend of the adsorption capacity is similar to the change trend of the selective adsorption effect.
4. Lithium extraction experiment of high magnesium-lithium ratio solution
In the process of extracting lithium from salt lake brine, Li is required to be selectively extracted from mixed ion solution with high magnesium-lithium ratio+. Therefore, selective extraction of lithium from the mixed solution with high magnesium-lithium ratio is an important index for examining the lithium ion selective adsorption film. Naturally evaporating and concentrating the salt lake brine, wherein Mg is contained in the salt lake brine2+The concentration is 74.9 g/L; li+The concentration was 0.15 g/L.
At temperatureAt 20 deg.C, preparing a mixture containing Mg2+And Li+Mixed solution of (2), Mg2+And Li+Respectively, of 74.9g/L and 0.15g/L, Mg in the initial mixed solution2+/Li+The mass ratio is 500:1, 10mg of the lithium ion selective adsorption film prepared in the embodiment 5 is placed in 30mL of mixed solution, soaked for 0.5h, then the lithium ion selective adsorption film is taken out to remove the solution on the surface of the film through centrifugation, then the lithium ion selective adsorption film is placed in 30mL of dilute hydrochloric acid solution with the concentration of 0.2mol/L for desorption treatment, the desorption time is 0.5h, and after the desorption is finished, an inductively coupled plasma emission spectrometer is used for measuring Li in the desorption solution+And Mg2+Concentration, calculating Mg in the desorbed liquid2+/Li+Mass ratio. After repeating the above six experiments, the high magnesium-lithium ratio solution can be changed into the low magnesium-lithium ratio solution.
For the first experiment: first mixed ion solution Mg2+/Li+The mass ratio is set as 500:1, wherein Mg2+The concentration is 74.9g/L (3mol/L), the membrane is soaked in the solution for selective adsorption, after the adsorption is finished, the membrane is soaked in the dilute hydrochloric acid solution for desorption, and Mg in the desorbed desorption solution is desorbed2+/Li+The mass ratio is 106: 1;
for the second experiment: second mixed solution Mg2+/Li+The mass ratio is set as 106:1, wherein Mg2+The concentration is still 74.9g/L (3mol/L), the membrane is soaked in the solution for selective adsorption, after the adsorption is finished, the membrane is soaked in the dilute hydrochloric acid solution for desorption, and Mg in the desorbed desorption solution is desorbed2+/Li+The mass ratio is 21: 1;
by analogy, according to the experimental process, after 6 times of cyclic tests, Mg in the desorbed solution is desorbed2+/Li+The mass ratio can be reduced to 0.7: 1.
The repeated experiment effect is shown in fig. 12, and fig. 12 is a graph of the result of the cycle lithium extraction experiment of the reduced graphene oxide film used in the solution with the high magnesium-lithium ratio in example 5 of the present invention. From the figure, it can be seen that the Mg of the initial high Mg/Li ratio solution2+/Li+The mass ratio is 500:1, and six experiments are carried outRear, Mg2+/Li+The mass ratio is reduced to 0.7:1, the mass ratio is reduced by nearly 3 orders of magnitude, and experimental results show that the lithium ion selective adsorption film can effectively and selectively extract Li from the solution of the mixed ion solution with high magnesium-lithium ratio+。
5. Experiment on stability of reduced graphene oxide film
3Mg of the lithium ion selective adsorption membrane prepared in example 5 was placed in 10mL of a lithium-magnesium mixed solution, wherein Mg is present2+The concentration is 79.4 g/L; li+The concentration is 0.15g/L, and the observation for 1-30 days shows that the observation shows that the lithium ion selective adsorption film after 1 day, 2 days, 5 days, 10 days, 15 days and 30 days is stable and does not swell, and can be used for Mg2+/Li+Adsorption experiments were selected.
Wherein the actual diagram of the reduced graphene oxide film is shown in fig. 13, and fig. 13 is a schematic diagram of the property of the reduced graphene oxide film changing with time in example 5 of the present invention. The figure shows that the reduced graphene oxide film does not swell, break and the like in the long-time soaking process, and the experimental result shows that the reduced graphene oxide film has stable property and can be circularly used in the lithium extraction process.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. The preparation method of the lithium ion selective adsorption membrane is characterized by comprising the following steps:
step one, preparing a graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by an oxidation stripping graphite method, wherein the suspended graphene sheet layer is about 0.5-1.0 nm in thickness of a monoatomic layer, and the sheet layer size diameter is 1-50 mu m;
step two, preparing a graphene oxide film: preparing the graphene oxide suspension prepared in the first step into a graphene oxide film by a dripping coating method, a suction filtration method and a spin coating method;
thirdly, thermal reduction: and (3) carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film.
2. The method for preparing a lithium ion selective adsorption membrane according to claim 1, wherein the concentration of the graphene oxide suspension is 1-6 mg/mL.
3. The method for preparing a lithium ion selective adsorption membrane according to claim 1, wherein the dropping method comprises the steps of: and dripping the graphene oxide suspension on the smooth paper surface, and drying to obtain the graphene oxide independent film.
4. The method for preparing a lithium ion selective adsorption membrane according to claim 1, wherein the suction filtration method comprises the steps of: carrying out suction filtration on the graphene oxide suspension, and drying the filter membrane to obtain a support membrane of the graphene oxide; wherein the suction filtration is filter membrane suction filtration; the pore diameter of the filter membrane is 0.22 μm, and the diameter is 38 mm.
5. The method for preparing a lithium ion selective adsorption membrane according to claim 1, wherein the spin coating method comprises the steps of: and (3) coating the graphene oxide suspension on a substrate, rotating the substrate to uniformly disperse the solution on the surface of the substrate, and drying the substrate to obtain the graphene oxide independent film.
6. The method for preparing the lithium ion selective adsorption membrane according to any one of claims 3 to 5, wherein the drying process comprises: drying for 1-24 h at the temperature of 50-70 ℃, repeatedly leaching with deionized water, then soaking in deionized water for 0.1-1 h, taking out, and drying for 1-24 h at the temperature of 50-70 ℃.
7. The method for preparing the lithium ion selective adsorption membrane according to claim 1, wherein the temperature of the high-temperature thermal reduction treatment is 100 to 180 ℃ and the time is 1 to 24 hours; the interlayer spacing of the lithium ion selective adsorption film is as follows: the interlayer spacing of the reduced graphene oxide film obtained by heat treatment at 140 ℃ and 180 ℃ is
Figure FDA0002648395510000011
8. Use of a lithium ion selective adsorption membrane prepared by the method of any one of claims 1 to 7 as a lithium ion adsorbent.
9. A lithium ion selective adsorption membrane prepared by the method of any one of claims 1 to 7 is used as a lithium ion adsorbent for selectively adsorbing lithium ions in salt lake brine.
10. The lithium ion selective adsorption membrane of claim 9, which is used as a lithium ion adsorbent to selectively adsorb lithium ions in salt lake brine, is characterized in that after evaporation and concentration of the salt lake brine, the mass ratio of magnesium ions to lithium ions is 1000: 1-0.5: 1.
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