CN114272888B - High-toughness lithium ion sieve composite hydrogel film, preparation method thereof and application thereof in extracting lithium from seawater - Google Patents
High-toughness lithium ion sieve composite hydrogel film, preparation method thereof and application thereof in extracting lithium from seawater Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation of high polymer materials, and provides a high-toughness lithium ion sieve composite hydrogel membrane, a preparation method thereof and application thereof in extracting lithium from seawater, wherein LiMn is obtained by reacting lithium hydroxide with hydrogen peroxide through a hydrothermal method, in order to solve the problems that the existing lithium ion sieve is in a powder shape, is not easy to recycle and has low adsorption rate 2 O 4 Obtaining lambda-MnO by acid washing 2 The method comprises the steps of carrying out a first treatment on the surface of the Heating polyvinyl alcohol PVA solution and dodecyl sodium sulfate SDS to react, and adding pyrrole and prepared lambda-MnO 2 Mixing with ammonium persulfate APS solution in ice water bath, pouring into a mold, and reacting at room temperature to obtain lambda-MnO 2 The @ interpenetrating gel composite membrane is soaked in deionized water and H is carried out in sequence 2 SO 4 Soaking in deionized water, washing, and drying to obtain the high-toughness lithium ion sieve composite hydrogel film.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a high-toughness lithium ion sieve composite hydrogel membrane, a preparation method thereof and application thereof in extracting lithium from seawater, wherein the high-toughness lithium ion sieve composite hydrogel membrane is prepared from lambda-MnO 2 As Li + Imprinting sites to prepare high-toughness porous lambda-MnO 2 An interpenetrating gel composite material.
Background
Lithium has been used for decades in the fields of ceramics, glass, rechargeable lithium batteries, nuclear fusion fuels, energy storage materials, and the like. As demand increases, meeting the provision of lithium resources is an important challenge. According to related researches, the lithium resource is mainly derived from ores, salt lakes and seawater, wherein Li in the seawater + The content is up to 2.6X10 14 kg, however, at a concentration of only 0.17ppm, the seawater also contains a large amount of coexisting alkali metal ions (Na + 、K + 、Ca 2+ 、Mg 2+ ) Thereby giving Li extraction + And presents great difficulties. HMO-based lithium ion sieves have excellent lithium selectivity, high lithium adsorption capacity, etc., and become one of the most popular lithium adsorbents, although HMO is specific to Li + The method has excellent selectivity, but when the method is applied to the lithium extraction by a physical method, the problem of restricting the practical application is that: mn is more dissolved and damaged during acid leaching; powder is easy to run off in the adsorption process; the adsorption time is longer.
Disclosure of Invention
The invention provides a high-toughness lithium ion sieve composite hydrogel membrane, a preparation method and application thereof in extracting lithium from seawater, and aims to solve the problems that the existing lithium ion sieve is in a powder shape, is not easy to recycle and has low adsorption rate, wherein the high-toughness lithium ion sieve composite hydrogel membrane is lambda-MnO 2 An interpenetrating gel composite film.
The invention is realized by the following technical scheme: a high-toughness lithium ion sieve composite hydrogel membrane is formed by coating interpenetrating polymer gel with lambda-MnO 2 Composite material, i.e. lambda-MnO 2 The @ interpenetrating gel composite material is prepared by reacting lithium hydroxide and hydrogen peroxide by a hydrothermal method 2 O 4 Obtaining lambda-MnO by acid washing 2 The method comprises the steps of carrying out a first treatment on the surface of the Heating polyvinyl alcohol PVA solution and dodecyl sodium sulfate SDS to react, and adding pyrrole and prepared lambda-MnO 2 Mixing with ammonium persulfate APS solution in ice water bath, pouring into a mold, and reacting at room temperature to obtain lambda-MnO 2 An interpenetrating gel composite film is provided,soaking in deionized water in turn, H 2 SO 4 Soaking in water, washing with deionized water, and drying to obtain lambda-MnO 2 An interpenetrating gel composite material.
The method for preparing the high-toughness lithium ion sieve composite hydrogel film comprises the following specific steps:
（1）LiMn 2 O 4 is prepared from the following steps: 3.45g of manganese acetate was dissolved in 30mL of deionized water to give an aqueous manganese acetate solution, 1.11g of lithium hydroxide was dissolved in 30mL of deionized water, and then 1.2mL of H was slowly added 2 O 2 Dripping into lithium hydroxide aqueous solution, dissolving the two solutions in 100mL of methanol solution, stirring for 18-22min, and reacting at 110deg.C by hydrothermal method for 12h to obtain LiMn 2 O 4 ；
（2）λ-MnO 2 Is prepared from the following steps: liMn obtained in step (1) 2 O 4 Washing with 0.5M HCl for 24 hr, alternately washing with deionized water and absolute ethanol until pH is neutral, and drying at 80deg.C to obtain lambda-MnO 2 A nanoparticle;
（3）λ-MnO 2 preparation of an interpenetrating gel composite film: dissolving polyvinyl alcohol PVA in deionized water, swelling for 1h at 60 ℃ and dissolving for 1h at 90 ℃ to prepare a polyvinyl alcohol aqueous solution with the mass concentration of 10%;
1.5-4.5g of 10% polyvinyl alcohol aqueous solution, 0.6-1.8g of deionized water and 115.3-350mg of sodium dodecyl sulfate SDS are mixed, heated and stirred at 50 ℃ for 1h until bubbles disappear, 70-210 mu L of pyrrole is added, stirred for 1h, hydrogel is fully dissolved, and lambda-MnO prepared in the step (2) is added 2 Stirring the nano particles for 1h to obtain a solution A;
228.2-684mg of APS is dissolved in 430 mu L of deionized water to obtain a solution B;
mixing the solution A and the solution B according to the volume ratio of 1:4, and then cooling to the temperature in an ice water bath<Quickly mixing at 5 ℃; pouring the mixture into a mold; reacting for 12h at room temperature to obtain lambda-MnO 2 An interpenetrating gel composite film;
（4）λ-MnO 2 obtaining an interpenetrating gel composite material: the lambda-MnO thus obtained was reacted with 2 Soaking the composite film in deionized water for 6h at 1M H 2 SO 4 Soaking for 2h, washing with deionized water, and lyophilizing to obtain lambda-MnO 2 An interpenetrating gel composite material.
In the solution A of the step (3), hydrogel and lambda-MnO are used 2 The total mass of the nano particles is calculated as benchmark, lambda-MnO 2 The mass ratio of the nano particles is 5% -40%.
Further, in the solution A in the step (3), hydrogel and lambda-MnO are used 2 The total mass of the nano particles is calculated as benchmark, lambda-MnO 2 The mass ratio of the nano particles is 5%, 15%, 25% or 35%.
Preferably, in the solution A of the step (3), the hydrogel is mixed with lambda-MnO 2 The total mass of the nano particles is calculated as benchmark, lambda-MnO 2 The mass ratio of the nano particles is 25%.
The freeze-drying process in step (4) was freeze-drying at a temperature of-83℃under a vacuum of 0.010 mbar.
The invention obtains a renewable lambda-MnO 2 Interpenetrating gel composite film and studied the adsorption of Li from Li solution and simulated seawater + The results show that lambda-MnO 2 The addition of (2) can reversely regulate the pore structure of the gel film, and 25 percent of lambda-MnO is formed by abundant pores and hydrophilicity 2 The adsorption content of the @ interpenetrating gel can be as high as 21.6 mg/g, furthermore, lambda-MnO 2 The @ interpenetrating gel composite membrane has high selectivity, has an extraction force of 94.1% in simulated seawater, and has high adsorption capacity under 5 adsorption-desorption cycles.
Drawings
FIG. 1 shows 25% lambda-MnO of three-dimensional porous structure 2 SEM image of @ interpenetrating gel composite film;
FIG. 2 is 25% lambda-MnO 2 EDS plot of @ interpenetrating gel composite membrane;
FIG. 3 is 25% lambda-MnO 2 A physical photograph of the @ interpenetrating gel composite film;
FIG. 4 shows lambda-MnO 2 Particles and different lambda-MnO 2 Curve of lithium ion adsorption quantity of interpenetrating gel composite film along with concentration changeA figure;
FIG. 5 is 25% lambda-MnO 2 The circularity of the @ interpenetrating gel composite film;
FIG. 6 is 25% lambda-MnO 2 Artificial seawater selectivity of @ interpenetrating gel composite membrane.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1: a high toughness lithium ion sieve composite hydrogel film, characterized in that: the high-toughness lithium ion sieve composite hydrogel film is formed by coating interpenetrating polymer gel with lambda-MnO 2 （λ-MnO 2 @interpenetrating gel) composite material is prepared by reacting lithium hydroxide with hydrogen peroxide through a hydrothermal method 2 O 4 Obtaining lambda-MnO by acid washing 2 The method comprises the steps of carrying out a first treatment on the surface of the Heating polyvinyl alcohol PVA solution and dodecyl sodium sulfate SDS to react, and adding pyrrole and prepared lambda-MnO 2 Mixing with ammonium persulfate APS solution in ice water bath, pouring into a mold, and reacting at room temperature to obtain lambda-MnO 2 The @ interpenetrating gel composite membrane is soaked in deionized water and H is carried out in sequence 2 SO 4 Soaking in water, washing with deionized water, and drying to obtain interpenetrating polymer gel coated lambda-MnO 2 （λ-MnO 2 @ interpenetrating gel) composite material.
The preparation method comprises the following steps:
（1）LiMn 2 O 4 is prepared from the following steps: 3.45 The manganese acetate g is dissolved in 30mL deionized water, the lithium hydroxide 1.11g is dissolved in 30mL deionized water, and then the H1.2 mL is slowly dripped 2 O 2 Then the two solutions are dissolved in a methanol solution of 100mL and stirred for about 20 min, and then are reacted at 110 ℃ for 12h by a hydrothermal method, finally the LiMn is prepared 2 O 4 ；
（2）λ-MnO 2 Is prepared from the following steps: liMn 2 O 4 Washing 24. 24h with 0.5M HCl, washing to neutrality with deionized water DI, and drying to obtain lambda-MnO 2 A nanoparticle;
（3）λ-MnO 2 preparation of an interpenetrating gel composite film: first, a 10% polyvinyl alcohol (PVA) solution was prepared, the PVA was dissolved in deionized water, swelled at 60℃for 1 hour, and then dissolved at 90℃for 1 hour. 10wt% PVA of 1.5-4.5g, deionized water of 0.6-1.8g and Sodium Dodecyl Sulfate (SDS) of 115.3-350mg were mixed and heated at 50℃for 1 hour until bubbles disappeared, to obtain solution A. Then 70-210 mu L of pyrrole is added and stirred for 1 hour to be fully dissolved in the solution A. After that, lambda-MnO is added 2 Powder, in the form of hydrogel with lambda-MnO 2 The total mass of the nano particles is calculated as benchmark, lambda-MnO 2 The mass ratio of the nano particles is 5% -40%; sequentially selecting: 5%, 15%, 25% or 35%; stirring is carried out again for 1 hour. Lithium ion sieve powder (lambda-MnO) 2 ) Compounding with a porous hydrogel film material.
The APS of 228.2-684mg was then dissolved in 430 μl of deionized water, referred to as solution B. The two solutions were cooled in an ice-water bath<5℃and then mixed rapidly. The mixture was then poured into a mold. The reaction was carried out at room temperature 12 h. Then the prepared lambda-MnO 2 The @ interpenetrating gel composite film was immersed in deionized water at 6h and then at 1M H 2 SO 4 Soaking in water 2 h. Washing with deionized water again, and lyophilizing at-83 deg.C under vacuum of 0.010mbar to obtain lambda-MnO 2 An interpenetrating gel composite film.
For the lambda-MnO obtained 2 For detection of the @ interpenetrating gel composite material, FIG. 1 shows a three-dimensional porous structure of 25% lambda-MnO 2 SEM image of @ interpenetrating gel composite film, and the result shows that lambda-MnO 2 The pore canal of the material is more uniform by adding, which is beneficial to Li ＋ Is removed from the mold; FIG. 2 is 25% lambda-MnO 2 Energy Dispersive Spectrometer (EDS) mapping of the interpenetrating gel composite film, through the EDS mapping, mn, C, O and other elements are found to exist, which confirms lambda-MnO 2 Uniformly dispersed in the hydrogel; FIG. 3 is 25% lambda-MnO 2 The physical photograph of the interpenetrating gel composite film can show that the material can be changed in different shapes according to the needs of researchers.
FIG. 4 shows lambda-MnO 2 Particles, interpenetrating gels and different lambda-MnO 2 Graph of adsorption quantity of lithium ions of interpenetrating gel composite film along with concentration change, and graph shows that the adsorption quantity of lithium ions along with lambda-MnO 2 The adsorption amount is gradually increased and 35% lambda-MnO 2 The adsorption amount was similar to that of particles (lambda-MnO) 2 Adsorption capacity is 26.41 mg/g,35% lambda-MnO 2 The adsorption capacity of the interpenetrating gel is 24.967 mg/g), so that the composite membrane solves the problem of adsorption capacity and the problem that powder is not easy to recycle.
FIG. 5 is 25% lambda-MnO 2 Recycling of the interpenetrating gel composite film, it can be seen that Li + The adsorption retention amount of (C) was relatively high, and there was only a decrease of less than 7 mg/g from the first cycle (22.3 mg/g) to the fifth cycle (15.2 mg/g), thus, 25% lambda-MnO 2 The @ interpenetrating gel has very good cycling stability.
FIG. 6 is 25% lambda-MnO 2 Artificial seawater selectivity of @ interpenetrating gel composite membrane, 25% lambda-MnO 2 Artificial seawater selectivity related data for the @ interpenetrating gel composite membrane are shown in table 3.
As shown in FIG. 6, 25% lambda-MnO 2 Extraction of Li from sea water by interpenetrating gel composite film + Is 94.1% more efficient than other metal ions (Ca 2+ 、K + 、Mg 2+ 、Na + Is less than 13.3%) and as can be seen from Table 3, li + The selection separation factor (Kd) of (C) is as high as 393.14 mg/g, and thus, the research result shows that 25% lambda-MnO 2 Interpenetrating gel composite film Li from simulated sea water + Has great application potential in selective separation. Ion sieve pairs of various Li-Mn-O systems + The adsorption performance of (c) is shown in table 1.
Table 1: ion sieve pairs of various Li-Mn-O systems + Adsorption performance comparison of (2)
lambda-MnO as obtained in example 1 2 Interpenetrating gel and lambda-MnO 2 BET surface area, pore volume, pore size data for the @ interpenetrating gel are shown in Table 2.
Table 2: lambda-MnO 2 Interpenetrating gel and lambda-MnO 2 BET surface area, pore volume, pore size data for @ interpenetrating gel
Table 3:25% lambda-MnO 2 Artificial seawater selectivity related data of @ interpenetrating gel composite membrane
Adsorption mechanism: currently, the proposed adsorption mechanisms mainly include redox mechanisms, ion exchange mechanisms, and redox and ion exchange complex mechanisms, and in the adsorption process, the present invention researches that LiMn 2 O 4 In eluting Li + What happens during (1) is the oxidation-reduction reaction, namely Mn 3+ Disproportionation reaction occurs in an acidic solution to produce Mn 2+ 、Mn 4+ Wherein the former remains in the spinel framework and the latter dissolves into the acidic solution, thus leaving behind corresponding sites after pickling, the spinel structure of the original precursor is maintained, three-dimensional ion channels (8a→16c→8a→16c) of specific dimensions are also formed, after which the material undergoes H during the adsorption process + And Li (lithium) + Is an ion exchange mechanism of (a).
Example 2: lambda-MnO in step (3) of this example 2 The mass ratio of powder to hydrogel was 0.91:2.73, the remainder of the procedure was as in example 1.
Example 3: in the step (2): liMn is added to 2 O 4 Fully divided into 0.5 and M of diluted hydrochloric acid, and Li is used as + /H + Washing with deionized water to neutrality at a molar ratio of 1:1 to obtain lambda-MnO by pickling 24h, washing with deionized water to neutrality, and drying at 90deg.C 2 A nanoparticle; in the step (3): lambda-MnO added to 0.91 g 2 The powder was stirred again for 1 hour; the rest of the procedure is as in example 1.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (6)
1. A high toughness lithium ion sieve composite hydrogel film, characterized in that: the high-toughness lithium ion sieve composite hydrogel film is formed by coating interpenetrating polymer gel with lambda-MnO 2 Composite material, i.e. lambda-MnO 2 Interpenetrating gel composite material, H 2 O 2 Dripping into lithium hydroxide aqueous solution, dissolving the solution and manganese acetate aqueous solution into methanol solution, and reacting by hydrothermal method to obtain LiMn 2 O 4 Obtaining lambda-MnO by acid washing 2 The method comprises the steps of carrying out a first treatment on the surface of the Heating polyvinyl alcohol PVA solution and dodecyl sodium sulfate SDS to react, and adding pyrrole and prepared lambda-MnO 2 Mixing with ammonium persulfate APS solution in ice water bath, pouring into a mold, and reacting at room temperature to obtain lambda-MnO 2 The @ interpenetrating gel composite membrane is soaked in deionized water and H is carried out in sequence 2 SO 4 Soaking in water, washing with deionized water, and drying to obtain lambda-MnO 2 An interpenetrating gel composite material.
2. A method of making the high toughness lithium ion sieve composite hydrogel film of claim 1, characterized by: the method comprises the following specific steps:
（1）LiMn 2 O 4 is prepared from the following steps: 3.45g of manganese acetate was dissolved in 30mL of deionized water to giveManganese acetate in water, 1.11g of lithium hydroxide was dissolved in 30mL of deionized water, and then 1.2mL of H was slowly added 2 O 2 Dripping into lithium hydroxide aqueous solution, dissolving the two solutions in 100mL of methanol solution, stirring for 18-22min, and reacting at 110deg.C by hydrothermal method for 12h to obtain LiMn 2 O 4 ；
（2）λ-MnO 2 Is prepared from the following steps: liMn obtained in step (1) 2 O 4 Washing with 0.5M HCl for 24 hr, alternately washing with deionized water and absolute ethanol until pH is neutral, and drying at 80deg.C to obtain lambda-MnO 2 A nanoparticle;
（3）λ-MnO 2 preparation of an interpenetrating gel composite film: dissolving polyvinyl alcohol PVA in deionized water, swelling for 1h at 60 ℃ and dissolving for 1h at 90 ℃ to prepare a polyvinyl alcohol aqueous solution with the mass concentration of 10%;
1.5-4.5g of 10% polyvinyl alcohol aqueous solution, 0.6-1.8g of deionized water and 115.3-350mg of sodium dodecyl sulfate SDS are mixed, heated and stirred at 50 ℃ for 1h until bubbles disappear, 70-210 mu L of pyrrole is added, stirred for 1h, hydrogel is fully dissolved, and lambda-MnO prepared in the step (2) is added 2 Stirring the nano particles for 1h to obtain a solution A;
228.2-684mg of APS is dissolved in 430 mu L of deionized water to obtain a solution B;
mixing the solution A and the solution B according to the volume ratio of 1:4, and then cooling to the temperature in an ice water bath<Quickly mixing at 5 ℃; pouring the mixture into a mold; reacting for 12h at room temperature to obtain lambda-MnO 2 An interpenetrating gel composite film;
（4）λ-MnO 2 obtaining an interpenetrating gel composite material: the lambda-MnO thus obtained was reacted with 2 Soaking the composite film in deionized water for 6h at 1M H 2 SO 4 Soaking for 2h, washing with deionized water, and lyophilizing to obtain lambda-MnO 2 An interpenetrating gel composite material.
3. The method of preparing a high toughness lithium ion sieve composite hydrogel film according to claim 2, wherein: step (3)In solution A, hydrogel and lambda-MnO 2 The total mass of the nano particles is calculated as benchmark, lambda-MnO 2 The mass ratio of the nano particles is 5% -40%.
4. A method of preparing a high toughness lithium ion sieve composite hydrogel film according to claim 3, wherein: in the solution A of the step (3), hydrogel and lambda-MnO are used 2 The total mass of the nano particles is calculated as benchmark, lambda-MnO 2 The mass ratio of the nano particles is 5%, 15%, 25% or 35%.
5. The method of preparing a high toughness lithium ion sieve composite hydrogel film according to claim 2, wherein: in the solution A of the step (3), hydrogel and lambda-MnO are used 2 The total mass of the nano particles is calculated as benchmark, lambda-MnO 2 The mass ratio of the nano particles is 25%.
6. The method of preparing a high toughness lithium ion sieve composite hydrogel film according to claim 2, wherein: the freeze-drying process in step (4) was freeze-drying at a temperature of-83℃under a vacuum of 0.010 mbar.
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