CN114100570B - Preparation method and application of lithium ion selective adsorption film - Google Patents

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

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CN114100570B
CN114100570B CN202010861793.1A CN202010861793A CN114100570B CN 114100570 B CN114100570 B CN 114100570B CN 202010861793 A CN202010861793 A CN 202010861793A CN 114100570 B CN114100570 B CN 114100570B
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graphene oxide
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selective adsorption
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CN114100570A (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: first, preparing graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by oxidizing and stripping graphite, wherein suspended graphene sheets are monoatomic layers with the thickness of about 0.5-1.0 nm, and the size and the diameter of the sheets are 1-50 mu m; secondly, preparing a graphene oxide film: preparing graphene oxide suspension prepared in the first step into a graphene oxide film by a dropping method, a suction filtration method, a spin coating method and the like; third, 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 provided by the invention is simple and easy to operate, and the prepared membrane is stable in property and not easy to crack, and has the effect of selectively adsorbing lithium ions.

Description

Preparation method and application of lithium ion selective adsorption film
Technical Field
The invention belongs to the technical field of preparation methods of lithium ion selective adsorption membranes and processes for extracting lithium from brine, and particularly relates to a preparation method of a lithium ion selective adsorption membrane capable of selectively adsorbing lithium ions in high-magnesium-lithium-ratio brine and application of the lithium ion selective adsorption membrane.
Background
Lithium is known as "Energy metal" and "metal pushing the world forward", and is widely Applied to the fields of lithium ion batteries (Advanced Functional Materials 2017,27;Nat Mater 2017,16,572-579;Nat Commun 2019,10,1081), storage devices (Science 2011,334,928-935;Nat Mater 2011,11,19-29), alloy technology (Nat Commun 2019,10,3428), glass (Sci Rep 2019,9,16607), ceramics (Journal of Power Sources 2013,228,250-255) and the like, and the application field of lithium is expanding, and the demand of lithium is increasing all over the world (Applied Energy 2013,110,252-266).
Lithium is mainly derived from solid lithium-containing ores and brine lithium resources, and almost 60% of the world's lithium is present in salt lake brine lithium resources, which are considered as the main source of lithium. However, most of the salt lake brine is Li + Concentration ofIs very low and coexists with a large amount of alkali metal and alkaline earth metal ions, and is similar in chemical properties, especially in ionic radius to Li + Closest Mg 2+ The content of magnesium and lithium in salt lakes is very high (hydrodynamics 2018,176,73-77), which makes it very difficult to separate and extract lithium therefrom.
There are many methods for extracting lithium from salt lake brine, mainly precipitation (Green Chemistry 2018,20,3121-3133), salting out (Journal of Membrane Science 2016,505,167-173), solvent extraction (hydrodynamics 2017,171,27-32), ion exchange adsorption (hydrodynamics 2010,102,37-42;Applied Surface Science 2018,427,931-941) and the like. Wherein the precipitation method has low purity of the product, 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; the solution extraction requires extractant, extraction base and corrosion resistant material, and is contaminated. The adsorption method has the advantages of simple process and high recovery rate, has certain advantages from the aspects of economy and environmental protection compared with other methods, and is particularly suitable for separating and extracting lithium from the 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 uses an organic ion adsorbent to adsorb Li by means of coulombic force + The method comprises the steps of carrying out a first treatment on the surface of the The inorganic ion adsorption method uses inorganic ion adsorbent to adsorb 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 adsorbents with good adsorption performance are powder-type, small in particle size, poor in fluidity and permeability, high in dissolution loss rate, difficult to granulate, and difficult to realize large-scale industrialization, and the actual lithium adsorption capacity of most adsorbents is still different from the theoretical maximum adsorption capacity of most adsorbents, so that the adsorbents are the problems to be solved in the process of extracting lithium by an adsorption method.
Disclosure of Invention
The invention aims to provide a preparation method of a lithium ion selective adsorption film, which solves the technical problems of difficult granulation, high dissolution loss rate, difficult realization of large-scale industrialization and the like of a lithium ion adsorbent in the prior art, and oxidized graphene film is treated by thermal reductionThe interlayer spacing of the reduced graphene oxide film is effectively controlled, and the interlayer spacing of the reduced graphene oxide film obtained by heat treatment at 140-180 ℃ isThe reduced graphene oxide membrane 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 high magnesium-lithium ratio.
The second object of the invention is to provide an application of the lithium ion selective adsorption film prepared by the method as a lithium ion adsorbent.
In order to achieve the above 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 film, comprising the following steps:
first, preparing graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by oxidizing and stripping graphite, wherein suspended graphene sheets are monoatomic layers with the thickness of about 0.5-1.0 nm, and the size and the diameter of the sheets are 1-50 mu m;
secondly, preparing a graphene oxide film: preparing graphene oxide suspension prepared in the first step into a graphene oxide film by a dropping method, a suction filtration method, a spin coating method and the like;
third, 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 the Hummers method, but is not limited to this oxidative exfoliation method.
The concentration of the graphene oxide suspension is 1-6 mg/mL, preferably 5mg/mL.
The graphene oxide film is a graphene oxide film conventionally used in the art, and can be an independent film or a support film of graphene oxide.
The graphene oxide film has a thickness of about 30 μm.
The dripping method is a conventional dripping method in the field, and the specific method comprises the following steps of: and (3) dripping graphene oxide suspension on the smooth paper surface, and drying to obtain the independent graphene oxide film.
The suction filtration method is a suction filtration method conventional in the art, and the specific method comprises the following steps: carrying out suction filtration on the graphene oxide suspension, and drying a filter membrane to obtain a support membrane of the graphene oxide; wherein the suction filtration is a filter membrane suction filtration; the filter is a filter conventionally used in the art, preferably an aqueous phase filter, having a pore size of 0.22 μm and a diameter of 38mm.
The spin coating method is a conventional spin coating method in the field, and the specific method comprises the following steps: and smearing 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 independent graphene oxide film.
The drying operation and conditions are those conventional in the art, and the drying process is as follows: drying at 50-70deg.C for 1-24 hr (preferably 60 deg.C for 12 hr), repeatedly eluting with deionized water, soaking in deionized water for 0.1-1 hr (preferably 0.5 hr), taking out, and drying at 50-70deg.C for 1-24 hr (preferably 60 deg.C for 6 hr).
The temperature of the high-temperature thermal reduction treatment is 100-180 ℃, preferably 140-180 ℃, more preferably 140 ℃; the time is 1 to 24 hours, preferably 1 to 4 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 140-180 ℃ is
The second aspect of the invention provides an application of the lithium ion selective adsorption film 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, which is used as a lithium ion adsorbent for selectively adsorbing lithium ions in salt lake brine.
After evaporating and concentrating the salt lake brine, the mass ratio of magnesium ions to lithium ions is 1000:1-0.5:1, preferably 500:1.
By adopting the technical scheme, the invention has the following advantages and beneficial effects:
the lithium ion selective adsorption film provided by the invention is a reduced graphene oxide film, on one hand, the carbon nanomaterial has a higher specific surface area, has a large adsorption capacity for lithium, and on the other hand, the selective adsorption effect for lithium ions in salt lake brine is good for high magnesium-lithium ratio.
The lithium ion selective adsorption film prepared by the method is a reduced graphene oxide film prepared by a thermal reduction method, the interlayer spacing of the reduced graphene oxide is effectively controlled, the efficient selective adsorption of lithium ions in a mixed salt solution is realized based on a size effect principle, and after six-cycle experiments are carried out by using the prepared reduced graphene oxide film, the Mg of a magnesium-lithium ion mixed solution 2+ /Li + The mass ratio is initially 500:1, finally desorbing the Mg of the obtained mixed solution 2+ /Li + The mass ratio is reduced to 0.7:1, the reduced graphene oxide film can effectively perform selective adsorption and desorption treatment on lithium ions in salt lake brine with high magnesium-lithium ratio. The preparation method provided by the invention is simple and easy to operate, and the prepared membrane is stable in property and not easy to crack, and has the effect of selectively adsorbing lithium ions. The invention also provides a process for extracting lithium from salt lake brine based on the reduced graphene oxide film, and the process has good application prospects in the fields of batteries, supercapacitors, automobiles, aerospace, metallurgy and the like.
Drawings
Fig. 1 is a schematic diagram of a physical photograph of a reduced graphene oxide film prepared by the method of the present invention.
FIG. 2 is a schematic representation of a scanning electron microscope-characterized surface topography of a reduced graphene oxide film prepared by the method of the present invention.
FIG. 3 is a schematic representation of a cross-sectional morphology of a scanning electron microscope characterization of a reduced graphene oxide film prepared using the method of the present invention.
Fig. 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 is a schematic representation of the immersion of reduced graphene oxide films in Mg in examples 1-9 of the present invention 2+ 、Li + XRD inter-layer distance data graphs of wet reduced graphene oxide films after 0.5h in the mixed solution of 1 mol/L.
FIG. 6 is a graph of Raman test spectra of reduced graphene oxide films in examples 1-9 of the present invention.
FIG. 7 is a graph showing the variation of the ratio of the D peak intensity to the G peak intensity in the Raman test spectra of the reduced graphene oxide films of examples 1 to 9 of the present invention.
FIG. 8 is Li + 、Mg 2+ Single ion solution adsorption capacity diagram.
FIG. 9 is a view showing the immersion of the reduced graphene oxide film in Li in examples 1 to 9 of the present invention + 、Mg 2+ The molar ratio is 1:1, and a selective adsorption effect change chart in the mixed solution.
FIG. 10 is a view showing the immersion of reduced graphene oxide films in Li in examples 1 to 9 of the present invention + 、Mg 2+ Li in the Mixed solution + Adsorption capacity change chart.
FIG. 11 is a view showing the immersion of reduced graphene oxide films in Li in examples 1 to 9 of the present invention + 、Mg 2+ Mg in mixed solution 2+ Adsorption capacity change chart.
Fig. 12 is a graph showing the results of the cyclic lithium extraction experiment of the reduced graphene oxide film for the high magnesium to lithium ratio solution in example 5 of the present invention.
Fig. 13 is a graph showing the property of the reduced graphene oxide film according to example 5 of the present invention with time.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
The preparation method of the lithium ion selective adsorption film comprises the following steps:
first, preparing 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 suspended graphene sheets are monoatomic layer thickness, about 0.5-1.0 nm, and the sheet size diameter is 1-50 mu m; the graphite powder was oxidized and exfoliated by Hummers method to obtain graphene oxide suspension, the concentration of which was 5mg/mL.
Secondly, preparing a graphene oxide film: the graphene oxide suspension prepared in the first step is prepared into an independent graphene oxide film by a dripping method, and the independent graphene oxide film is specifically prepared as follows:
1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step is dripped on a smooth paper sheet, and is dried for 12 hours in a 60 ℃ oven, an independent graphene oxide film is taken down, the graphene oxide film is repeatedly leached by deionized water, is taken out after being soaked in a large amount of deionized water for half an hour, is dried for 6 hours in the oven with the temperature of 60 ℃, and is put into a drying dish for use, and the thickness of the obtained graphene oxide film is about 30 mu m.
Third, thermal reduction: carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step in an oven with the temperature of 100 ℃ for 1-4h to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film, which is named as rGO-100, wherein the XRD detects the layer spacing of the dried reduced graphene oxide film, and the reduced graphene oxide film isSoaking the dried reduced graphene oxide film in mixed Mg 2+ 、Li + Obtaining a wet reduced graphene oxide film in the ion solution, and XRD detecting the interlayer spacing of the wet reduced graphene oxide film to be +.>
Example 2
The preparation method of the lithium ion selective adsorption film comprises the following steps:
first, preparing graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by oxidizing and stripping graphite, wherein suspended graphene sheets are monoatomic layers with the thickness of about 0.5-1.0 nm, and the size and the diameter of the sheets are 1-50 mu m; the graphite powder was oxidized and exfoliated by Hummers method to obtain graphene oxide suspension, the concentration of which was 5mg/mL.
Secondly, preparing a graphene oxide film: the graphene oxide suspension prepared in the first step is prepared into an independent graphene oxide film by a dripping method, and the independent graphene oxide film is specifically prepared as follows:
1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step is dripped on a smooth paper sheet, and is dried for 12 hours in a 60 ℃ oven, an independent graphene oxide film is taken down, the graphene oxide film is repeatedly leached by deionized water, is taken out after being soaked in a large amount of deionized water for half an hour, is dried for 6 hours in the oven with the temperature of 60 ℃, and is put into a drying dish for use, and the thickness of the obtained graphene oxide film is about 30 mu m.
Third, thermal reduction: carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step in an oven with the temperature of 110 ℃ for 1-4h to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film, which is named as rGO-110, wherein the XRD detects the layer spacing of the dried reduced graphene oxide film, and the reduced graphene oxide film isSoaking the dried reduced graphene oxide film in mixed Mg 2+ 、Li + Obtaining a wet reduced graphene oxide film in the ion solution, and XRD detecting the interlayer spacing of the wet reduced graphene oxide film to be +.>
Example 3
The preparation method of the lithium ion selective adsorption film comprises the following steps:
first, preparing graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by oxidizing and stripping graphite, wherein suspended graphene sheets are monoatomic layers with the thickness of about 0.5-1.0 nm, and the size and the diameter of the sheets are 1-50 mu m; the graphite powder was oxidized and exfoliated by Hummers method to obtain graphene oxide suspension, the concentration of which was 5mg/mL.
Secondly, preparing a graphene oxide film: the graphene oxide suspension prepared in the first step is prepared into an independent graphene oxide film by a dripping method, and the independent graphene oxide film is specifically prepared as follows:
1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step is dripped on a smooth paper sheet, and is dried for 12 hours in a 60 ℃ oven, an independent graphene oxide film is taken down, the graphene oxide film is repeatedly leached by deionized water, is taken out after being soaked in a large amount of deionized water for half an hour, is dried for 6 hours in the oven with the temperature of 60 ℃, and is put into a drying dish for use, and the thickness of the obtained graphene oxide film is about 30 mu m.
Third, thermal reduction: carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step in an oven with the temperature of 120 ℃ for 1-4h to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film, which is named rGO-120, wherein the XRD detection of the layer spacing of the dried reduced graphene oxide film is thatSoaking the dried reduced graphene oxide film in mixed Mg 2+ 、Li + Obtaining a wet reduced graphene oxide film in the ion solution, and XRD detecting the interlayer spacing of the wet reduced graphene oxide film to be +.>
Example 4
The preparation method of the lithium ion selective adsorption film comprises the following steps:
first, preparing graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by oxidizing and stripping graphite, wherein suspended graphene sheets are monoatomic layers with the thickness of about 0.5-1.0 nm, and the size and the diameter of the sheets are 1-50 mu m; the graphite powder was oxidized and exfoliated by Hummers method to obtain graphene oxide suspension, the concentration of which was 5mg/mL.
Secondly, preparing a graphene oxide film: the graphene oxide suspension prepared in the first step is prepared into an independent graphene oxide film by a dripping method, and the independent graphene oxide film is specifically prepared as follows:
1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step is dripped on a smooth paper sheet, and is dried for 12 hours in a 60 ℃ oven, an independent graphene oxide film is taken down, the graphene oxide film is repeatedly leached by deionized water, is taken out after being soaked in a large amount of deionized water for half an hour, is dried for 6 hours in the oven with the temperature of 60 ℃, and is put into a drying dish for use, and the thickness of the obtained graphene oxide film is about 30 mu m.
Third, thermal reduction: carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step in an oven with the temperature of 130 ℃ for 1-4h to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film, which is named rGO-130, wherein the XRD detection of the layer spacing of the dried reduced graphene oxide film is thatSoaking the dried reduced graphene oxide film in mixed Mg 2+ 、Li + Obtaining a wet reduced graphene oxide film in the ion solution, and XRD detecting the interlayer spacing of the wet reduced graphene oxide film to be +.>
Example 5
The preparation method of the lithium ion selective adsorption film comprises the following steps:
first, preparing graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by oxidizing and stripping graphite, wherein suspended graphene sheets are monoatomic layers with the thickness of about 0.5-1.0 nm, and the size and the diameter of the sheets are 1-50 mu m; the graphite powder was oxidized and exfoliated by Hummers method to obtain graphene oxide suspension, the concentration of which was 5mg/mL.
Secondly, preparing a graphene oxide film: the graphene oxide suspension prepared in the first step is prepared into an independent graphene oxide film by a dripping method, and the independent graphene oxide film is specifically prepared as follows:
1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step is dripped on a smooth paper sheet, and is dried for 12 hours in a 60 ℃ oven, an independent graphene oxide film is taken down, the graphene oxide film is repeatedly leached by deionized water, is taken out after being soaked in a large amount of deionized water for half an hour, is dried for 6 hours in the oven with the temperature of 60 ℃, and is put into a drying dish for use, and the thickness of the obtained graphene oxide film is about 30 mu m.
Third, thermal reduction: carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step in an oven with the temperature of 140 ℃ for 1-4h to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film, which is named as rGO-140, wherein the XRD detection of the layer spacing of the dried reduced graphene oxide film is thatSoaking the dried reduced graphene oxide film in mixed Mg 2+ 、Li + Obtaining a wet reduced graphene oxide film in the ion solution, and XRD detecting the interlayer spacing of the wet reduced graphene oxide film to be +.>
Example 6
The preparation method of the lithium ion selective adsorption film comprises the following steps:
first, preparing graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by oxidizing and stripping graphite, wherein suspended graphene sheets are monoatomic layers with the thickness of about 0.5-1.0 nm, and the size and the diameter of the sheets are 1-50 mu m; the graphite powder was oxidized and exfoliated by Hummers method to obtain graphene oxide suspension, the concentration of which was 5mg/mL.
Secondly, preparing a graphene oxide film: the graphene oxide suspension prepared in the first step is prepared into an independent graphene oxide film by a dripping method, and the independent graphene oxide film is specifically prepared as follows:
1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step is dripped on a smooth paper sheet, and is dried for 12 hours in a 60 ℃ oven, an independent graphene oxide film is taken down, the graphene oxide film is repeatedly leached by deionized water, is taken out after being soaked in a large amount of deionized water for half an hour, is dried for 6 hours in the oven with the temperature of 60 ℃, and is put into a drying dish for use, and the thickness of the obtained graphene oxide film is about 30 mu m.
Third, thermal reduction: carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step in an oven with the temperature of 150 ℃ for 1-4h to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film, which is named rGO-150, wherein the XRD detects the layer spacing of the dried reduced graphene oxide film to beSoaking the dried reduced graphene oxide film in mixed Mg 2+ 、Li + Obtaining a wet reduced graphene oxide film in the ion solution, and XRD detecting the interlayer spacing of the wet reduced graphene oxide film to be +.>
Example 7
The preparation method of the lithium ion selective adsorption film comprises the following steps:
first, preparing graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by oxidizing and stripping graphite, wherein suspended graphene sheets are monoatomic layers with the thickness of about 0.5-1.0 nm, and the size and the diameter of the sheets are 1-50 mu m; the graphite powder was oxidized and exfoliated by Hummers method to obtain graphene oxide suspension, the concentration of which was 5mg/mL.
Secondly, preparing a graphene oxide film: the graphene oxide suspension prepared in the first step is prepared into an independent graphene oxide film by a dripping method, and the independent graphene oxide film is specifically prepared as follows:
1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step is dripped on a smooth paper sheet, and is dried for 12 hours in a 60 ℃ oven, an independent graphene oxide film is taken down, the graphene oxide film is repeatedly leached by deionized water, is taken out after being soaked in a large amount of deionized water for half an hour, is dried for 6 hours in the oven with the temperature of 60 ℃, and is put into a drying dish for use, and the thickness of the obtained graphene oxide film is about 30 mu m.
Third, thermal reduction: carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step in an oven with the temperature of 160 ℃ for 1-4h to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film, which is named as rGO-160, wherein the XRD detects the layer spacing of the dried reduced graphene oxide film, namely the reduced graphene oxide film isSoaking the dried reduced graphene oxide film in mixed Mg 2+ 、Li + Obtaining a wet reduced graphene oxide film in the ion solution, and XRD detecting the interlayer spacing of the wet reduced graphene oxide film to be +.>
Example 8
The preparation method of the lithium ion selective adsorption film comprises the following steps:
first, preparing graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by oxidizing and stripping graphite, wherein suspended graphene sheets are monoatomic layers with the thickness of about 0.5-1.0 nm, and the size and the diameter of the sheets are 1-50 mu m; the graphite powder was oxidized and exfoliated by Hummers method to obtain graphene oxide suspension, the concentration of which was 5mg/mL.
Secondly, preparing a graphene oxide film: the graphene oxide suspension prepared in the first step is prepared into an independent graphene oxide film by a dripping method, and the independent graphene oxide film is specifically prepared as follows:
1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step is dripped on a smooth paper sheet, and is dried for 12 hours in a 60 ℃ oven, an independent graphene oxide film is taken down, the graphene oxide film is repeatedly leached by deionized water, is taken out after being soaked in a large amount of deionized water for half an hour, is dried for 6 hours in the oven with the temperature of 60 ℃, and is put into a drying dish for use, and the thickness of the obtained graphene oxide film is about 30 mu m.
Third, thermal reduction: carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step in an oven with the temperature of 170 ℃ for 1-4h to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film, which is named rGO-170, wherein the XRD detects the layer spacing of the dried reduced graphene oxide film to beSoaking the dried reduced graphene oxide film in mixed Mg 2+ 、Li + Obtaining a wet reduced graphene oxide film in the ion solution, and XRD detecting the interlayer spacing of the wet reduced graphene oxide film to be +.>
Example 9
The preparation method of the lithium ion selective adsorption film comprises the following steps:
first, preparing graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by oxidizing and stripping graphite, wherein suspended graphene sheets are monoatomic layers with the thickness of about 0.5-1.0 nm, and the size and the diameter of the sheets are 1-50 mu m; the graphite powder was oxidized and exfoliated by Hummers method to obtain graphene oxide suspension, the concentration of which was 5mg/mL.
Secondly, preparing a graphene oxide film: the graphene oxide suspension prepared in the first step is prepared into an independent graphene oxide film by a dripping method, and the independent graphene oxide film is specifically prepared as follows:
1mL of the graphene oxide solution with the concentration of 5mg/mL prepared in the first step is dripped on a smooth paper sheet, and is dried for 12 hours in a 60 ℃ oven, an independent graphene oxide film is taken down, the graphene oxide film is repeatedly leached by deionized water, is taken out after being soaked in a large amount of deionized water for half an hour, is dried for 6 hours in the oven with the temperature of 60 ℃, and is put into a drying dish for use, and the thickness of the obtained graphene oxide film is about 30 mu m.
Third, thermal reduction: carrying out high-temperature thermal reduction treatment on the graphene oxide film prepared in the second step in an oven with the temperature of 180 ℃ for 1-4h to obtain a reduced graphene oxide film, namely the lithium ion selective adsorption film, which is named rGO-180, wherein the XRD detection of the layer spacing of the dried reduced graphene oxide film is thatSoaking the dried reduced graphene oxide film in mixed Mg 2+ 、Li + Obtaining a wet reduced graphene oxide film in the ion solution, and XRD detecting the interlayer spacing of the wet reduced graphene oxide film to be +.>
Characterization test of reduced graphene oxide film prepared by the embodiment of the invention:
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) for XRD detection, ranging from 5-30℃with a step size of 0.15 ℃.
The reduced graphene oxide films prepared in examples 1-9 were characterized by Raman, and Raman detection was performed by HR 800.
The physical photo morphology diagram of the reduced graphene oxide film is shown in fig. 1, and fig. 1 is a schematic diagram of the physical photo of the reduced graphene oxide film prepared by the method of the invention. SEM electron micrographs are shown in fig. 2 and 3, fig. 2 is a schematic view of the surface morphology of the reduced graphene oxide film prepared by the method of the present invention, and fig. 3 is a schematic view of the cross-sectional morphology of the reduced graphene oxide film prepared by the method of the present invention. The porous structure of the reduced graphene oxide can be seen from the figure.
XRD characterization patterns are shown in FIGS. 4 and 5, FIG. 4 being an implementation of the present inventionXRD inter-layer spacing data patterns of the dried reduced graphene oxide films of examples 1-9. FIG. 5 is a schematic representation of the immersion of reduced graphene oxide films in Mg in examples 1-9 of the present invention 2+ 、Li + XRD inter-layer distance data graphs of wet reduced graphene oxide films after 0.5h in the mixed solution of 1 mol/L. As can be seen from the figure, the film spacing of the reduced graphene oxide film after the high temperature heat treatment at 140-180 ℃ is obviously reduced
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 variation of the ratio of the D peak intensity to the G peak intensity in the Raman test spectra of the reduced graphene oxide films of examples 1 to 9 of the present invention. As can be seen from the graph, the D peak (. About.1352 cm) -1 ) Is a defect peak, G peak (-1570 cm) -1 ) Is a characteristic peak of crystalline carbon, and the ratio of the D peak to G peak intensity (ID/IG) of the rGO film is continuously increased along with the increase of the reduction temperature, so that defects in the reduced graphene oxide film are continuously increased.
2. Lithium ion selective adsorption membranes are respectively used for Mg 2+ 、Li + Adsorption experiments of solutions
At a temperature of 20deg.C, 10mg of the lithium ion selective adsorption film prepared in example 5 was placed in 30mL of initial Li + Soaking in LiCl solution with the concentration of 1mol/L for 0.5h, taking out the lithium ion selective adsorption film, centrifuging to remove the film surface solution, then placing the lithium ion selective adsorption film in 30mL of dilute hydrochloric acid solution with the concentration of 0.2mol/L for desorption treatment, wherein the desorption time is 0.5h, and measuring Li in the desorption solution by using an inductively coupled plasma emission spectrometer after the desorption is completed + The concentration and the adsorption amount were calculated. The calculation formula is as follows
Q Li ＝C Li ×V/m
Wherein Q is Li Is Li + Is a gas-liquid separation device; c (C) Li Li is a desorption solution + Concentration; v is the volume of desorption solution; m is the mass of the adsorption film.
At a temperature of 20 DEG C10Mg of the lithium ion selective adsorption film prepared in example 5 was placed in 30mL of initial Mg 2+ MgCl with concentration of 1mol/L 2 Soaking in the solution for 0.5h, taking out the lithium ion selective adsorption membrane, centrifuging to remove the membrane surface solution, then placing the lithium ion selective adsorption membrane in 30mL of 0.2mol/L dilute hydrochloric acid solution for desorption treatment, wherein the desorption time is 0.5h, and measuring the Mg in the desorption solution by using an inductively coupled plasma emission spectrometer after the desorption is completed 2+ The concentration and the adsorption amount were calculated. The calculation formula is as follows
Q Mg ＝C Mg ×V/m
Wherein Q is Mg Is Mg 2+ Is a gas-liquid separation device; c (C) Mg Mg being a desorption solution 2+ Concentration; v is the volume of desorption solution; m is the mass of the adsorption film.
Wherein the adsorption amount is as shown in FIG. 8, FIG. 8 is Li + 、Mg 2+ Single ion solution adsorption capacity diagram. As can be seen from the figure, the lithium ion selective adsorption film was effective for Li when the initial solution ion concentration was 1mol/L + Adsorption capacity was 10.4Mg/g (1.51 mmol/g), relative to Mg 2+ The adsorption amount was 38.4mg/g (1.58 mmol/g). The experimental result shows that in a single ion solution, the selective adsorption film of lithium ion for Li + And Mg (magnesium) 2+ The adsorption molar ratio of (2) is almost the same.
3、Mg 2+ /Li + Selective adsorptivity test
In a practical industrial process, selective extraction of Li from a large amount of mixed ion solution is required + . Therefore, the selective adsorption performance is an important index for examining the lithium ion selective adsorption film.
At a temperature of 20 ℃, li-containing components are arranged + And Mg (magnesium) 2+ Is a mixed solution of Li + And Mg (magnesium) 2+ 10mg of the lithium ion selective adsorption film prepared in examples 1-9 is placed in 30mL of mixed solution, soaked for 0.5h, then the solution on the surface of the film is removed by 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 the solution is used after the desorption is completedInductively coupled plasma emission spectrometer for measuring Li in desorption solution + And Mg (magnesium) 2+ The concentration, selective adsorption performance and adsorption amount were calculated.
The adsorption performance calculation formula is as follows
K 0 ＝1
Ke＝C Mg /C Li
Wherein K is 0 Is Mg in the initial mixed solution 2+ /Li + Molar ratio, ratio is 1; ke is Mg in desorption solution 2+ /Li + Molar ratio; c (C) Mg Mg being a desorption solution 2+ Concentration, C Li Li is a desorption solution + Concentration;
as shown in FIG. 9, FIG. 9 is a view showing the immersion of the reduced graphene oxide film in Li in examples 1 to 9 of the present invention + 、Mg 2+ The molar ratio is 1:1, and a selective adsorption effect change chart in the mixed solution. Immersing the reduced graphene oxide films of examples 1-9 in Mg 2+ /Li + The molar ratio is 1:1, soaking the reduced graphene oxide film in a dilute hydrochloric acid solution for desorption after the adsorption is finished, and measuring Li in the desorption solution by using an inductively coupled plasma emission spectrometer + And Mg (magnesium) 2+ Concentration and Mg 2+ /Li + Molar ratio. It can be seen from the figure that Mg as the heat treatment temperature increases from 100 ℃ to 140 °c 2+ /Li + The molar ratio is continuously reduced, which indicates that the reduced graphene oxide film is used for Li + The selective adsorption effect of (a) is continuously increased; as the heat treatment temperature increases from 140℃to 180℃Mg 2+ /Li + The molar ratio slightly increased, indicating that the reduced graphene oxide film was resistant to Li + The selective adsorption effect of (a) is reduced. The experimental result shows that the reduced graphene oxide film obtained by heat treatment at 140 ℃ has the best effect of selectively adsorbing lithium ions.
The adsorption amount calculation formula is as follows
Q Li ＝C Li ×V/m
Q Mg ＝C Mg ×V/m
Wherein Q is Li Is Li + Is a gas-liquid separation device; c (C) Li Li is a desorption solution + Concentration; q (Q) Mg Is Mg 2+ Is a gas-liquid separation device; c (C) Mg Mg being a desorption solution 2+ Concentration; v is the volume of desorption solution; m is the mass of the adsorption film.
Wherein the adsorption amounts are shown in FIG. 10 and FIG. 11, FIG. 10 shows that the reduced graphene oxide films of examples 1 to 9 of the present invention are immersed in Li + 、Mg 2+ Li in the Mixed solution + FIG. 11 is a graph showing the change in adsorption capacity, in which reduced graphene oxide films of examples 1 to 9 of the present invention were immersed in Li + 、Mg 2+ Mg in mixed solution 2+ Adsorption capacity change chart. From the graph, it can be seen that as the heat treatment temperature is increased, the adsorption capacity of the reduced graphene oxide film is changed, and the adsorption capacity change trend is similar to the selective adsorption effect change trend.
4. High magnesium-lithium ratio solution lithium extraction experiment
In the extraction of lithium from salt lake brine, the selective extraction of Li from mixed ion solution with high magnesium-lithium ratio is always required + . Therefore, the selective extraction of lithium from the mixed solution with high magnesium-lithium ratio is an important index for examining the selective adsorption film of lithium ions. Naturally evaporating and concentrating salt lake brine, wherein Mg 2+ The concentration is 74.9g/L; li (Li) + The concentration was 0.15g/L.
The Mg-containing alloy is prepared under the condition of 20 DEG C 2+ And Li (lithium) + Mg of (d) 2+ And Li (lithium) + The initial concentrations of (2) are 74.9g/L and 0.15g/L, respectively, of Mg in the initial mixture solution 2+ /Li + Placing 10mg of the lithium ion selective adsorption film prepared in the example 5 into 30mL of mixed solution with the mass ratio of 500:1, soaking for 0.5h, taking out the lithium ion selective adsorption film, centrifuging to remove the film surface solution, placing the lithium ion selective adsorption film into 30mL of dilute hydrochloric acid solution with the concentration of 0.2mol/L for desorption treatment, wherein the desorption time is 0.5h, and measuring Li in the desorption solution by using an inductively coupled plasma emission spectrometer after the desorption is completed + And Mg (magnesium) 2+ Concentration, calculating Mg in desorption liquid 2+ /Li + Mass ratio. After repeating the above six experiments, high magnesium lithiumThe specific solution can be changed into a low magnesium-lithium specific solution.
First experiment: first mixed ion solution Mg 2+ /Li + The mass ratio is set to 500:1, wherein Mg 2+ The concentration is 74.9g/L (3 mol/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 solution after desorption 2+ /Li + The mass ratio is 106:1;
second experiment: second mixed solution Mg 2+ /Li + The mass ratio is set to 106:1, wherein Mg 2+ The concentration is still 74.9g/L (3 mol/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 the Mg in the desorbed solution after the desorption 2+ /Li + The mass ratio is 21:1;
similarly, according to the experimental flow, after 6 times of cyclic tests, mg in the desorbed solution after desorption 2+ /Li + The mass ratio can be reduced to 0.7:1.
The repeated experimental effects are shown in fig. 12, and fig. 12 is a graph of the experimental results of the cyclic lithium extraction of the reduced graphene oxide film for the high magnesium-lithium ratio solution in example 5 of the present invention. From the figure it can be seen that the Mg of the initial high magnesium to lithium ratio solution 2+ /Li + The mass ratio is 500:1, and after six experiments, mg is added 2+ /Li + The mass ratio is reduced to 0.7:1, which is reduced by about 3 orders of magnitude, and experimental results show that the lithium ion selective adsorption film can effectively extract Li from the mixed ion solution with high magnesium-lithium ratio in a solution selective way + 。
5. Reduced graphene oxide film stability experiments
3Mg of the lithium ion-selective adsorption film prepared in example 5 was placed in 10mL of a lithium-magnesium mixed solution in which Mg 2+ The concentration is 79.4g/L; li (Li) + The concentration of the lithium ion selective adsorption film is 0.15g/L, and after observation for 1-30 days, the result is shown in figure 13, and the lithium ion selective adsorption film is stable and unswollen after being respectively subjected to 1 day, 2 days, 5 days, 10 days, 15 days and 30 days, and can be used for Mg 2+ /Li + Adsorption experiments were selected.
Wherein a physical diagram of the reduced graphene oxide film is shown as 13, and fig. 13 is a schematic diagram showing the property change of the reduced graphene oxide film with time in embodiment 5 of the present invention. The graph shows that the reduced graphene oxide film has no swelling, breakage and other phenomena in the long-time soaking process, and experimental results show that the reduced graphene oxide film has stable properties and can be recycled in the lithium extraction process.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.

Claims (9)

1. Use of a selective adsorption membrane as a lithium ion adsorbent;
wherein the preparation method of the selective adsorption film comprises the following steps:
first, preparing graphene oxide suspension: the graphene oxide suspension is a graphene oxide solution prepared by oxidizing and stripping graphite, wherein suspended graphene sheets are monoatomic layers with the thickness of 0.5-1.0 nm and the size and the diameter of the sheets of 1-50 mu m;
secondly, preparing a graphene oxide film: preparing graphene oxide suspension prepared in the first step into a graphene oxide film by a dropping method, a suction filtration method and a spin coating method;
third, thermal reduction: 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 a lithium ion selective adsorption film;
the temperature of the high-temperature thermal reduction treatment is 100-180 ℃ and the time is 1-24 h.
2. The use according to claim 1, wherein the selective adsorption membrane selectively adsorbs lithium ions in salt lake brine as a lithium ion adsorbent.
3. The use according to claim 2, wherein the mass ratio of magnesium lithium ions after evaporation and concentration of the salt lake brine is 1000:1-0.5:1.
4. Use according to any one of claims 1 to 3, wherein the concentration of graphene oxide suspension is 1mg/mL to 6mg/mL.
5. A use according to any one of claims 1 to 3, wherein the dispensing process comprises the steps of: and (3) dripping graphene oxide suspension on the smooth paper surface, and drying to obtain the independent graphene oxide film.
6. A use according to any one of claims 1 to 3, wherein the suction filtration process comprises the steps of: carrying out suction filtration on the graphene oxide suspension, and drying a filter membrane to obtain a support membrane of the graphene oxide; wherein the suction filtration is a filter membrane suction filtration; the pore size of the filter membrane is 0.22 μm, and the diameter is 38mm.
7. Use according to any one of claims 1 to 3, wherein the spin coating method comprises the steps of: and smearing 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 independent graphene oxide film.
8. A use according to any one of claims 1 to 3, wherein the drying process is: drying for 1-24 h at 50-70 ℃, repeatedly leaching with deionized water, soaking in the deionized water for 0.1-1 h, taking out, and drying for 1-24 h at 50-70 ℃.
9. Use according to any one of claims 1 to 3, wherein the interlayer spacing of the lithium ion selective adsorption membrane is: the interlayer spacing of the reduced graphene oxide film obtained by heat treatment at 140-180 ℃ is 3.7 A+/-0.1A.
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