CN113351180B - Preparation method and application of temperature response type bionic lithium ion imprinting composite membrane - Google Patents

Preparation method and application of temperature response type bionic lithium ion imprinting composite membrane Download PDF

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CN113351180B
CN113351180B CN202110639912.3A CN202110639912A CN113351180B CN 113351180 B CN113351180 B CN 113351180B CN 202110639912 A CN202110639912 A CN 202110639912A CN 113351180 B CN113351180 B CN 113351180B
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lithium ion
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李正
何广泽
毕嘉楠
牟航葵
牛静东
张兰河
张海丰
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Electric Power Research Institute of State Grid Jilin Electric Power Co Ltd
Northeast Electric Power University
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Abstract

A preparation method and application of a temperature response type bionic lithium ion imprinting composite membrane relate to a preparation method and application of a lithium ion imprinting composite membrane. The invention aims to solve the problems that an acidic desorption reagent causes irreversible damage to adsorption sites and generates a large amount of elution wastewater in the preparation and application processes of the conventional bionic lithium ion imprinted composite membrane. The method comprises the following steps: firstly, preparing a PDA @ PVDF film; secondly, preparing a PDA @ PVDF-RAFT film; thirdly, preparing a PDA @ PVDF-RAFT-PDEA film; and fourthly, preparing Li-TSIIM. Temperature response type bionic lithium ion imprinting composite membrane for absorbing Li+. The temperature response type bionic lithium ion imprinted composite membrane prepared by the invention has better selective adsorption capacity on lithium ions, and has the characteristics of strong reproducibility and good chemical stability. The temperature response type bionic lithium ion imprinting composite membrane can be obtained.

Description

Preparation method and application of temperature response type bionic lithium ion imprinting composite membrane
Technical Field
The invention relates to a preparation method and application of a lithium ion imprinting composite membrane.
Background
Lithium ion batteries, which are rechargeable batteries in the 90 s of the 20 th century, are widely used in portable devices such as mobile phones, notebook computers, and digital cameras. Meanwhile, the electric vehicle is gradually popularized in military affairs, medical treatment and the field of electric vehicles. At present, China becomes a large country for the production, consumption and export of lithium ion batteries.
With the popularity of lithium ion batteries in various industries, the global demand for lithium has seen explosive growth. Approximately 2550 ten thousand tons of Li resources are available globally, and are depleted in approximately 15 years, as calculated by the current usage rate. Therefore, from the viewpoint of environmental protection and energy consumption, it is of great significance to recover resources from waste lithium batteries. The conventional method for recovering lithium from waste lithium ion batteries mainly comprises a chemical method and a solvent extraction method. However, the chemical method for recovering lithium not only has a complex process, but also has a large impact on the environment along with the use of a large amount of chemicals; most of the solvent extraction methods adopt organic solvents as background solvents, so that the price is high, fire disasters are easy to cause, and the safety coefficient is low. Therefore, a novel recovery technology with safety, reliability and simple process is needed for Li in waste lithium ion batteries+And carrying out selective recycling.
As a new selective separation and purification technology, the bionic ion imprinting membrane is expected to selectively and directly separate and recover Li resources in complex waste lithium ion battery leachate. Compared with the common chemical precipitation, solvent extraction and other modes at present, the bionic ion imprinting membrane has the advantages of high selectivity, good separation effect and strong reusability, and has great significance for direct selective recovery of Li resources of waste lithium ion batteries and solving of the problem of insufficient Li resources in the world at present. However, in the preparation and application process of the existing bionic ion imprinting membrane, template ions (Li) must be removed by acid washing+) Removal, which not only causes irreversible damage to the adsorption sites, but is also accompanied by the production of large amounts of elution waste.
Disclosure of Invention
The invention aims to solve the problems that an acidic desorption reagent causes irreversible damage to adsorption sites and generates a large amount of elution wastewater in the preparation and application processes of the conventional bionic lithium ion imprinted composite membrane, and provides a preparation method and application of a temperature response type bionic lithium ion imprinted composite membrane.
A preparation method of a temperature response type bionic lithium ion imprinting composite membrane is completed according to the following steps:
firstly, preparing a PDA @ PVDF film:
dissolving trihydroxymethyl aminomethane in deionized water, adjusting the pH value to be alkaline, adding dopamine hydrochloride and a PVDF membrane, stirring, taking out the PVDF membrane after stirring, washing the PVDF membrane by using the deionized water, and drying to obtain a PDA @ PVDF membrane;
secondly, preparing a PDA @ PVDF-RAFT film:
dissolving 4-dimethylaminopyridine and trithiocarbonate into dichloromethane, adding a PDA @ PVDF membrane, adding dicyclohexylcarbodiimide under the protection of a nitrogen atmosphere, sealing a reaction system, reacting under the conditions of the nitrogen atmosphere, stirring and ice bath, taking out the PVDF membrane after the reaction is finished, cleaning, and finally drying to obtain the PDA @ PVDF-RAFT membrane;
thirdly, preparing a PDA @ PVDF-RAFT-PDEA film:
adding the PDA @ PVDF-RAFT membrane into a mixed solution of N, N-diethyl-2-acrylamide, azodiisobutyronitrile and 1, 4-dioxane, introducing nitrogen, sealing a reaction system, reacting under the conditions of nitrogen atmosphere and stirring, taking out the PVDF membrane after the reaction is finished, cleaning, and finally drying to obtain the PDA @ PVDF-RAFT-PDEA membrane;
fourthly, preparing Li-TSIIM:
adding LiCl and 12-crown-4 into methanol, and stirring to obtain a mixed solution; putting the PDA @ PVDF-RAFT-PDEA film into the mixed solution, adding azodiisobutyronitrile, ethylene glycol dimethacrylate and methacrylic acid, introducing nitrogen, sealing the reaction system, stirring in a nitrogen atmosphere, performing condensation reflux at the temperature of 75 ℃, taking out the PVDF film after the reaction is finished, cleaning, and finally drying to obtain Li-TSIIM, namely the temperature response type bionic lithium ion imprinting composite film.
Temperature response type bionic lithium ion imprinting composite membrane for absorbing Li+。
The principle of the invention is as follows:
n, N-diethyl-2-acrylamide (DEA) is a common temperature-sensitive material, and the critical temperature of the material is 32 ℃. When T is<At 32 ℃, the polymer PDEA is in an expanded state; when T is>At 32 ℃ PDEA was in a contracted state (shown in FIG. 1). Therefore, DEA is grafted as a temperature-sensitive functional monomer through the polymerization reaction of reversible addition fragmentation chain transfer (RAFT) in the process of preparing the temperature-responsive bionic lithium ion imprinted composite membrane to form PDEA, and then the PDEA is grafted with Li+The functional monomer 12-crown ether-4 and methacrylic acid with specific recognition function endow the bionic lithium ion imprinted membrane with a temperature response function. The invention is characterized in that at T<PDEA is in an expanded state at 32 ℃ so that the grafted 12-crown-4 and methacrylic acid are far away from Li+(shown in FIG. 1), the desorption of Li is achieved+The effect of (1); in contrast, at T>At 32 ℃, PDEA is in a shrinkage state, so that the grafted 12-crown-4 and methacrylic acid are close to Li+To Li+The effect of adsorption is achieved. By endowing the bionic lithium ion imprinted membrane with the temperature response effect, the problem that the acid washing is adopted to carry out the Li in the preparation and use processes of the bionic lithium ion imprinted membrane is avoided+The desorption is carried out, thereby avoiding the irreversible damage of acidic eluent to adsorption sites and the generation of a large amount of elution wastewater.
The invention has the beneficial effects that:
the invention provides a preparation method of a temperature response type bionic lithium ion imprinting composite membrane (Li-TSIIM), which adopts a PVDF membrane as a base membrane, takes PDA formed by self-polymerization of dopamine hydrochloride (DA) as an interface adhesion layer, and prepares the temperature response type bionic lithium ion imprinting membrane by grafting a temperature-sensitive functional monomer N, N-diethyl-2-acrylamide (DEA) and 12-crown ether-4 and methacrylic acid (MAA) which have specific recognition effects on lithium ions;
the temperature response type bionic lithium ion imprinted composite membrane (Li-TSIIM) prepared by the method changes the process of desorbing lithium ions by using an acid washing imprinted membrane in the traditional process; the temperature is adopted for carrying out adsorption and desorption on lithium ions, so that a large amount of elution wastewater is avoided, and the damage to adsorption sites of the bionic blotting membrane can be reduced;
the temperature response type bionic lithium ion imprinting composite membrane (Li-TSIIM) prepared by the invention has good selective adsorption capacity on lithium ions, and has the characteristics of strong reproducibility and good chemical stability.
The temperature response type bionic lithium ion imprinting composite membrane can be obtained.
Drawings
FIG. 1 is a process diagram of preparing a temperature-responsive biomimetic lithium ion imprinted composite membrane according to example 1;
FIG. 2 is a SEM photograph showing a PVDF membrane as a component a, a PDA @ PVDF membrane as prepared in step one of example 1 as a component b, a PDA @ PVDF-RAFT membrane as prepared in step two of example 1 as a component c, a PDA @ PVDF-RAFT-PDEA membrane as prepared in step three of example 1 as a component d, and a Li-TSIIM as prepared in step four of example 1 as a component d.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the embodiment is a preparation method of a temperature response type bionic lithium ion imprinting composite membrane, which is completed according to the following steps:
firstly, preparing a PDA @ PVDF film:
dissolving trihydroxymethyl aminomethane in deionized water, adjusting the pH value to be alkaline, adding dopamine hydrochloride and a PVDF membrane, stirring, taking out the PVDF membrane after stirring, washing the PVDF membrane by using the deionized water, and drying to obtain a PDA @ PVDF membrane;
secondly, preparing a PDA @ PVDF-RAFT film:
dissolving 4-dimethylaminopyridine and trithiocarbonate into dichloromethane, adding a PDA @ PVDF membrane, adding dicyclohexylcarbodiimide under the protection of a nitrogen atmosphere, sealing a reaction system, reacting under the conditions of the nitrogen atmosphere, stirring and ice bath, taking out the PVDF membrane after the reaction is finished, cleaning, and finally drying to obtain the PDA @ PVDF-RAFT membrane;
thirdly, preparing a PDA @ PVDF-RAFT-PDEA film:
adding the PDA @ PVDF-RAFT membrane into a mixed solution of N, N-diethyl-2-acrylamide, azodiisobutyronitrile and 1,4 dioxane, introducing nitrogen, sealing a reaction system, reacting under the conditions of nitrogen atmosphere and stirring, taking out the PVDF membrane after the reaction is finished, cleaning, and finally drying to obtain the PDA @ PVDF-RAFT-PDEA membrane;
fourthly, preparing Li-TSIIM:
adding LiCl and 12-crown-4 into methanol, and stirring to obtain a mixed solution; putting the PDA @ PVDF-RAFT-PDEA film into the mixed solution, adding azodiisobutyronitrile, ethylene glycol dimethacrylate and methacrylic acid, introducing nitrogen, sealing the reaction system, performing condensation reflux under the nitrogen atmosphere and at the temperature of 75 ℃, taking out the PVDF film after the reaction is finished, cleaning, and finally drying to obtain Li-TSIIM, namely the temperature response type bionic lithium ion imprinting composite film.
The trihydroxymethyl aminomethane adopted in the technical proposal is taken as a buffer reagent;
dopamine hydrochloride (DA) adopted by the technical scheme is used as an interface adhesion material;
4-dimethylamino pyridine (DMAP) adopted in the technical scheme is used as a reaction catalyst;
the trithiocarbonate (RAFT reagent) adopted by the technical scheme is used as a chain transfer reagent synthetic material;
the dichloromethane, 1,4 dioxane and methanol adopted by the technical scheme are used as background solvents for reaction;
the dicyclohexylcarbodiimide adopted in the technical scheme is used as a low-temperature dehydrating agent;
the N, N-diethyl-2-acrylamide (DEA) adopted in the technical scheme is used as a temperature-sensitive functional monomer;
the Azobisisobutyronitrile (AIBN) adopted in the technical scheme is used as a free radical initiator;
the LiCl adopted in the technical scheme has the function of providing Li template+；
The Ethylene Glycol Dimethacrylate (EGDMA) adopted in the technical scheme is taken as a cross-linking agent for reaction;
the 12-crown-4 and methacrylic acid (MAA) adopted in the technical scheme are used as functional monomers with specific recognition function on lithium ions.
Static adsorption experiment:
adding a certain amount of Li-TSIIM into the corresponding test solution, oscillating in a constant-temperature water bath at the temperature of 35 ℃, and inspecting different Li+Li-TSIIM vs Li at initial concentration+The adsorption capacity of (1). After the adsorption is finished, measuring the residual Li in the test solution by adopting an inductively coupled plasma generation spectrometer (ICP)+And the adsorption capacity Q is tested based on the resultt(mg/g)。
Figure BDA0003106584670000041
In the formula C0(mg/L) and Ct(mg/L) is Li in the solution before and after adsorption respectively+M (g) is the amount of Li-TSIIM added, and V (mL) is the volume of the test solution.
Selective adsorption experiments:
taking a certain amount of Li-TSIIM and adding Li+And Co2+In the mixed solution of (1), at 35 DEG CAfter oscillating in a constant temperature water bath for a certain time at the temperature of (1), investigating Co2+With interference of Li-TSIIM on Li+Selective adsorption performance of. Testing Li-TSIIM vs Li+And Co2+The method of adsorption capacity is the same as the static adsorption experiment.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the volume ratio of the mass of the trihydroxymethyl aminomethane to the deionized water in the step one (0.1 g-0.15 g) is 60 mL; the volume ratio of the mass of the dopamine hydrochloride to the deionized water in the step one (0.2 g-0.25 g) is 60 mL; the PVDF film in the first step has the diameter of 47mm and the thickness of 0.45 μm. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the alkaline pH value in the first step is 8.5; the stirring speed in the step one is 30 r/min-60 r/min, and the stirring time is 6 h-8 h; in the first step, the PVDF membrane is washed by deionized water for 3 to 5 times, and then dried for 1 to 2 hours at the temperature of between 50 and 70 ℃ to obtain the PDA @ PVDF membrane. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the volume ratio of the mass of the 4-dimethylamino pyridine to the dichloromethane in the step two (0.3 g-0.5 g) is 15 mL; the volume ratio of the mass of the trithiocarbonate to the volume of the methylene dichloride in the step two is (0.15 g-0.2 g) 15 mL; the volume ratio of the mass of the dicyclohexylcarbodiimide to the dichloromethane in the second step is (10 g-15 g):15 mL. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: and in the second step, reacting for 20-24 h under the conditions of nitrogen atmosphere, stirring speed of 60-90 r/min and ice bath, taking out the PVDF membrane after the reaction is finished, alternately cleaning the PVDF membrane by using deionized water and absolute ethyl alcohol for 3-5 times, and finally drying for 8-12 h at the temperature of 35-45 ℃ to obtain the PDA @ PVDF-RAFT membrane. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: in the mixed solution of N, N-diethyl-2-acrylamide, azobisisobutyronitrile and 1,4 dioxane in the third step, the mass ratio of N, N-diethyl-2-acrylamide to azobisisobutyronitrile is 0.1:0.15, and the volume ratio of N, N-diethyl-2-acrylamide to 1,4 dioxane is 0.1g:20 mL. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: in the third step, the reaction is carried out for 18 to 24 hours under the conditions of nitrogen gas and stirring, and the reaction temperature is between 70 and 75 ℃; and after the reaction is finished, taking out the PVDF membrane, alternately cleaning the PVDF membrane by using deionized water and absolute ethyl alcohol for 3-5 times, and finally drying for 8-12 hours at the temperature of 35-45 ℃ to obtain the PDA @ PVDF-RAFT-PDEA membrane. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the volume ratio of the LiCl to the methanol in the step four is (0.3 g-0.7 g) to 90 mL; the volume ratio of the 12-crown-4 to the methanol in the step four (0.3 mL-0.7 mL) is 90 mL; in the fourth step, LiCl and 12-crown-4 are added into methanol, and then stirred for 0.5 to 2 hours at the stirring speed of 60 to 90 r/min; the volume ratio of the mass of the azodiisobutyronitrile to the methanol in the step four (0.1 g-0.2 g) is 90 mL; the volume ratio of the ethylene glycol dimethacrylate to the methanol in the step four (0.3 mL-0.7 mL) is 90 mL; the volume ratio of the methacrylic acid to the methanol in the fourth step (0.3 mL-0.7 mL) is 90 mL. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: and in the fourth step, the condensation reflux is carried out for 16 h-24 h under the nitrogen atmosphere, the stirring speed is 30 r/min-60 r/min and the temperature is 75 ℃, after the reaction is finished, the PVDF membrane is taken out, the PVDF membrane is alternately cleaned by deionized water and absolute ethyl alcohol for 3-5 times, and finally dried for 8 h-12 h at the temperature of 35-45 ℃ to obtain the Li-TSIIM, namely the temperature response type bionic lithium ion imprinted composite membrane. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the temperature response type bionic lithium ion imprinting composite membrane is used for absorbing Li+。
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: a preparation method of a temperature response type bionic lithium ion imprinting composite membrane is completed according to the following steps:
firstly, preparing a PDA @ PVDF film:
firstly, dissolving 0.1g of tris (hydroxymethyl) aminomethane in 60mL of deionized water, then adjusting the pH to 8.5, then adding 0.2g of dopamine hydrochloride and a piece of PVDF membrane, finally stirring for 6 hours at a stirring speed of 60r/min, taking out the PVDF membrane after stirring is finished, washing the PVDF membrane for 3 times by using deionized water, and drying for 1 hour at a temperature of 60 ℃ to obtain the PDA @ PVDF membrane;
the PVDF film in the first step has the diameter of 47mm and the thickness of 0.45 μm;
secondly, preparing a PDA @ PVDF-RAFT film:
dissolving 0.3g of 4-dimethylaminopyridine and 0.15g of trithiocarbonate into 15mL of dichloromethane, adding a PDA @ PVDF membrane, adding 10g of dicyclohexylcarbodiimide under the protection of a nitrogen atmosphere, sealing a reaction system, reacting for 24 hours under the conditions of the nitrogen atmosphere, the stirring speed of 60r/min and an ice bath, taking out the PVDF membrane after the reaction is finished, cleaning the PVDF membrane by using deionized water and absolute ethyl alcohol alternately for 3 times, and drying for 12 hours at the temperature of 45 ℃ to obtain the PDA @ PVDF-RAFT membrane;
thirdly, preparing a PDA @ PVDF-RAFT-PDEA film:
adding the PDA @ PVDF-RAFT membrane into a mixed solution of N, N-diethyl-2-acrylamide, azodiisobutyronitrile and 1, 4-dioxane, introducing nitrogen, sealing a reaction system, reacting for 24 hours at the temperature of 70 ℃ under the nitrogen atmosphere and at the stirring speed of 60r/min, taking out the PVDF membrane after the reaction is finished, alternately cleaning the PVDF membrane by using deionized water and absolute ethyl alcohol for 3 times, and finally drying for 12 hours at the temperature of 45 ℃ to obtain the PDA @ PVDF-RAFT-PDEA membrane;
the mixed solution of the N, N-diethyl-2-acrylamide, the azobisisobutyronitrile and the 1,4 dioxane in the third step is formed by mixing 0.1g N of N-diethyl-2-acrylamide, 0.15g of azobisisobutyronitrile and 20mL of 1,4 dioxane;
fourthly, preparing Li-TSIIM:
adding 0.3g LiCl and 0.3mL 12-crown-4 into 90mL methanol, and stirring at the stirring speed of 60r/min for 2h to obtain a mixed solution; putting the PDA @ PVDF-RAFT-PDEA film into the mixed solution, adding 0.1g of azobisisobutyronitrile, 0.3mL of ethylene glycol dimethacrylate and 0.3mL of methacrylic acid, introducing nitrogen, sealing the reaction system, carrying out condensation reflux for 16h under the nitrogen atmosphere at a stirring speed of 60r/min and at a temperature of 75 ℃, taking out the PVDF film after the reaction is finished, alternately cleaning the PVDF film by using deionized water and absolute ethyl alcohol for 3 times, and finally drying at a temperature of 45 ℃ for 12h to obtain Li-TSIIM, namely the temperature response type bionic lithium ion imprinting composite film.
Static adsorption experiment: 6 parts of Li-TSIIM prepared in example 1 are weighed, respectively placed into 6 centrifuge tubes, 10mL of LiCl solution is added, the concentration is respectively 5mg/L, 10mg/L, 20mg/L, 50mg/L, 100mg/L and 200mg/L, and then the mixture is shaken in a constant temperature water area for 3 hours at 35 ℃. After the adsorption is finished, measuring the residual Li in the test solution by using an Inductively Coupled Plasma (ICP) spectrometer+And the adsorption capacity Q is tested based on the resultt(mg/g)。
The results show that in Li+At a concentration of 200mg/L, the adsorption capacity of Li-TSIIM is the largest, and the maximum saturated adsorption capacity is 38.85 mg/g.
Selective adsorption experiments: 0.1g of Li-TSIIM prepared in example 1 was charged with 100mL of Li-containing solution+And Co2+The concentration of two ions in the mixed solution is 50mg/L, and the concentration of the two ions is examined in Co after the mixed solution is shaken in a constant-temperature water bath at the temperature of 35 ℃ for a certain time2+With interference of Li-TSIIM on Li+Selective adsorption performance of.
The results show that, in the mixed solution, examples1 preparation of Li-TSIIM vs Li+Has an adsorption capacity of 36.54mg/g for Co2+The adsorption capacity of (A) was 8.4mg/g, demonstrating that Li-TSIIM is responsible for Li+Has high selectivity.
Example 2: a preparation method of a temperature response type bionic lithium ion imprinting composite membrane is completed according to the following steps:
firstly, preparing a PDA @ PVDF film:
firstly, dissolving 0.1g of tris (hydroxymethyl) aminomethane in 60mL of deionized water, then adjusting the pH to 8.5, then adding 0.2g of dopamine hydrochloride and a piece of PVDF membrane, finally stirring for 6 hours at a stirring speed of 60r/min, taking out the PVDF membrane after stirring is finished, washing the PVDF membrane for 3 times by using deionized water, and drying for 1 hour at a temperature of 60 ℃ to obtain the PDA @ PVDF membrane;
the PVDF film in the first step has the diameter of 47mm and the thickness of 0.45 μm;
secondly, preparing a PDA @ PVDF-RAFT film:
dissolving 0.3g of 4-dimethylaminopyridine and 0.15g of trithiocarbonate into 15mL of dichloromethane, adding a PDA @ PVDF membrane, adding 10g of dicyclohexylcarbodiimide under the protection of a nitrogen atmosphere, sealing a reaction system, reacting for 24 hours under the conditions of the nitrogen atmosphere, the stirring speed of 60r/min and an ice bath, taking out the PVDF membrane after the reaction is finished, alternately cleaning the PVDF membrane by using deionized water and absolute ethyl alcohol for 3 times, and finally drying for 12 hours at the temperature of 45 ℃ to obtain the PDA @ PVDF-RAFT membrane;
thirdly, preparing a PDA @ PVDF-RAFT-PDEA film:
adding the PDA @ PVDF-RAFT membrane into a mixed solution of N, N-diethyl-2-acrylamide, azodiisobutyronitrile and 1, 4-dioxane, introducing nitrogen, sealing a reaction system, reacting for 24 hours at the temperature of 70 ℃ under the nitrogen atmosphere and at the stirring speed of 60r/min, taking out the PVDF membrane after the reaction is finished, alternately cleaning the PVDF membrane by using deionized water and absolute ethyl alcohol for 3 times, and finally drying for 12 hours at the temperature of 45 ℃ to obtain the PDA @ PVDF-RAFT-PDEA membrane;
the mixed solution of the N, N-diethyl-2-acrylamide, the azobisisobutyronitrile and the 1,4 dioxane in the third step is formed by mixing 0.3g N of N-diethyl-2-acrylamide, 0.15g of azobisisobutyronitrile and 20mL of 1,4 dioxane;
fourthly, preparing Li-TSIIM:
adding 0.3g LiCl and 0.5mL 12-crown-4 into 90mL methanol, and stirring at the stirring speed of 60r/min for 2h to obtain a mixed solution; putting the PDA @ PVDF-RAFT-PDEA film into the mixed solution, adding 0.1g of azobisisobutyronitrile, 0.3mL of ethylene glycol dimethacrylate and 0.3mL of methacrylic acid, introducing nitrogen, sealing the reaction system, carrying out condensation reflux for 16h under the nitrogen atmosphere at a stirring speed of 60r/min and at a temperature of 75 ℃, taking out the PVDF film after the reaction is finished, alternately cleaning the PVDF film by using deionized water and absolute ethyl alcohol for 3 times, and finally drying at a temperature of 45 ℃ for 12h to obtain Li-TSIIM, namely the temperature response type bionic lithium ion imprinting composite film.
Static adsorption experiment: 6 parts of Li-TSIIM prepared in example 2 are weighed, respectively placed into 6 centrifuge tubes, 10mL of LiCl solution is added, the concentration is respectively 5mg/L, 10mg/L, 20mg/L, 50mg/L, 100mg/L and 200mg/L, and then shaking is carried out in a constant temperature water area for 3h under the condition of 35 ℃. After the adsorption is finished, measuring the residual Li in the test solution by using an Inductively Coupled Plasma (ICP) spectrometer+And the adsorption capacity Q is tested based on the resultt(mg/g)。
The results show that in Li+At a concentration of 200mg/L, the adsorption capacity of Li-TSIIM was the largest, and the maximum saturated adsorption capacity was 42.58 mg/g.
Selective adsorption experiments: 0.1g of Li-TSIIM prepared in example 2 was charged with 100mL of Li-containing solution+And Co2+The concentration of two ions in the mixed solution is 50mg/L, and the concentration of the two ions is examined in Co after the mixed solution is shaken in a constant-temperature water bath at the temperature of 35 ℃ for a certain time2+With interference of Li-TSIIM on Li+Selective adsorption performance of.
The results show that in the mixed solution, Li-TSIIM is added to Li+Has an adsorption capacity of 40.58mg/g for Co2+The adsorption capacity of (A) was 11.2mg/g, demonstrating that Li-TSIIM is responsible for Li+Has high selectivity.
Example 3: a preparation method of a temperature response type bionic lithium ion imprinting composite membrane is completed according to the following steps:
firstly, preparing a PDA @ PVDF film:
firstly, dissolving 0.1g of tris (hydroxymethyl) aminomethane in 60mL of deionized water, then adjusting the pH to 8.5, then adding 0.2g of dopamine hydrochloride and a piece of PVDF membrane, finally stirring at a stirring speed of 60r/min for 6 hours, taking out the PVDF membrane after stirring is finished, washing the PVDF membrane with deionized water for 3 times, and drying at the temperature of 60 ℃ for 1 hour to obtain the PDA @ PVDF membrane;
the PVDF film in the first step has the diameter of 47mm and the thickness of 0.45 μm;
secondly, preparing a PDA @ PVDF-RAFT film:
dissolving 0.3g of 4-dimethylaminopyridine and 0.15g of trithiocarbonate into 15mL of dichloromethane, adding a PDA @ PVDF membrane, adding 10g of dicyclohexylcarbodiimide under the protection of a nitrogen atmosphere, sealing a reaction system, reacting for 24 hours under the conditions of the nitrogen atmosphere, the stirring speed of 60r/min and an ice bath, taking out the PVDF membrane after the reaction is finished, cleaning the PVDF membrane by using deionized water and absolute ethyl alcohol alternately for 3 times, and drying for 12 hours at the temperature of 45 ℃ to obtain the PDA @ PVDF-RAFT membrane;
thirdly, preparing a PDA @ PVDF-RAFT-PDEA film:
adding the PDA @ PVDF-RAFT membrane into a mixed solution of N, N-diethyl-2-acrylamide, azodiisobutyronitrile and 1, 4-dioxane, introducing nitrogen, sealing a reaction system, reacting for 24 hours at the temperature of 70 ℃ under the nitrogen atmosphere and at the stirring speed of 60r/min, taking out the PVDF membrane after the reaction is finished, alternately cleaning the PVDF membrane by using deionized water and absolute ethyl alcohol for 3 times, and finally drying for 12 hours at the temperature of 45 ℃ to obtain the PDA @ PVDF-RAFT-PDEA membrane;
the mixed solution of the N, N-diethyl-2-acrylamide, the azobisisobutyronitrile and the 1,4 dioxane in the third step is formed by mixing 0.5g N of N-diethyl-2-acrylamide, 0.15g of azobisisobutyronitrile and 20mL of 1,4 dioxane;
fourthly, preparing Li-TSIIM:
adding 0.3g LiCl and 0.7mL 12-crown-4 into 90mL methanol, and stirring at the stirring speed of 60r/min for 2h to obtain a mixed solution; putting the PDA @ PVDF-RAFT-PDEA film into the mixed solution, adding 0.1g of azobisisobutyronitrile, 0.3mL of ethylene glycol dimethacrylate and 0.3mL of methacrylic acid, introducing nitrogen, sealing the reaction system, carrying out condensation reflux for 16h under the nitrogen atmosphere at a stirring speed of 60r/min and at a temperature of 75 ℃, taking out the PVDF film after the reaction is finished, alternately cleaning the PVDF film by using deionized water and absolute ethyl alcohol for 3 times, and finally drying at a temperature of 45 ℃ for 12h to obtain Li-TSIIM, namely the temperature response type bionic lithium ion imprinting composite film.
Static adsorption experiment: static adsorption experiment: 6 parts of Li-TSIIM prepared in example 3 are weighed, respectively placed into 6 centrifuge tubes, 10mL of LiCl solution is added, the concentration is respectively 5mg/L, 10mg/L, 20mg/L, 50mg/L, 100mg/L and 200mg/L, and then the mixture is shaken in a constant temperature water area for 3 hours at 35 ℃. After the adsorption is finished, measuring the residual Li in the test solution by using an Inductively Coupled Plasma (ICP) spectrometer+And the adsorption capacity Q is tested based on the resultt(mg/g)。
The results show that in Li+At a concentration of 200mg/L, the adsorption capacity of Li-TSIIM was the largest, and the maximum saturated adsorption capacity was 39.76 mg/g.
Selective adsorption experiments: 0.1g of Li-TSIIM prepared in example 3 was added to 100mL of a solution containing Li+And Co2+In the mixed solution, the concentrations of two ions are both 50mg/L, and after oscillating in a constant-temperature water bath at the temperature of 35 ℃ for a certain time, the concentration of the two ions is examined in Co2+With interference of Li-TSIIM on Li+Selective adsorption performance of.
The results show that in the mixed solution, Li-TSIIM is added to Li+Has an adsorption capacity of 38.45mg/g for Co2+The adsorption capacity of (A) was 10.88mg/g, demonstrating that Li-TSIIM is responsible for Li+Has high selectivity.

Claims (7)

1. A preparation method of a temperature response type bionic lithium ion imprinting composite membrane is characterized in that the preparation method of the temperature response type bionic lithium ion imprinting composite membrane is completed according to the following steps:
firstly, preparing a PDA @ PVDF film:
dissolving trihydroxymethyl aminomethane in deionized water, adjusting the pH value to be alkaline, adding dopamine hydrochloride and a PVDF membrane, stirring, taking out the PVDF membrane after stirring, washing the PVDF membrane by using the deionized water, and drying to obtain a PDA @ PVDF membrane;
secondly, preparing a PDA @ PVDF-RAFT film:
dissolving 4-dimethylaminopyridine and trithiocarbonate into dichloromethane, adding a PDA @ PVDF membrane, adding dicyclohexylcarbodiimide under the protection of a nitrogen atmosphere, sealing a reaction system, reacting under the conditions of the nitrogen atmosphere, stirring and ice bath, taking out the PVDF membrane after the reaction is finished, cleaning, and finally drying to obtain the PDA @ PVDF-RAFT membrane;
the volume ratio of the mass of the 4-dimethylamino pyridine to the dichloromethane in the step two (0.3 g-0.5 g) is 15 mL;
the volume ratio of the mass of the trithiocarbonate to the dichloromethane in the step two is (0.15 g-0.2 g) 15 mL;
the volume ratio of the mass of the dicyclohexylcarbodiimide to the dichloromethane in the step two is (10 g-15 g) 15 mL;
thirdly, preparing a PDA @ PVDF-RAFT-PDEA film:
adding the PDA @ PVDF-RAFT membrane into a mixed solution of N, N-diethyl-2-acrylamide, azodiisobutyronitrile and 1, 4-dioxane, introducing nitrogen, sealing a reaction system, reacting under the conditions of nitrogen atmosphere and stirring, taking out the PVDF membrane after the reaction is finished, cleaning, and finally drying to obtain the PDA @ PVDF-RAFT-PDEA membrane;
in the third step, the mass ratio of the N, N-diethyl-2-acrylamide to the azobisisobutyronitrile in the mixed solution of the N, N-diethyl-2-acrylamide, the azobisisobutyronitrile and the 1,4 dioxane is 0.1:0.15, and the volume ratio of the mass of the N, N-diethyl-2-acrylamide to the 1,4 dioxane is 0.1g:20 mL; in the third step, the reaction is carried out for 18 to 24 hours under the conditions of nitrogen atmosphere and stirring, and the reaction temperature is between 70 and 75 ℃;
fourthly, preparing Li-TSIIM:
adding LiCl and 12-crown-4 into methanol, and stirring to obtain a mixed solution; putting the PDA @ PVDF-RAFT-PDEA film into the mixed solution, adding azodiisobutyronitrile, ethylene glycol dimethacrylate and methacrylic acid, introducing nitrogen, sealing a reaction system, stirring in a nitrogen atmosphere, performing condensation reflux at the temperature of 75 ℃, taking out the PVDF film after the reaction is finished, cleaning, and finally drying to obtain Li-TSIIM, namely the temperature response type bionic lithium ion imprinting composite film;
the volume ratio of the LiCl to the methanol in the step four is (0.3 g-0.7 g) to 90 mL;
the volume ratio of the 12-crown-4 to the methanol in the step four (0.3 mL-0.7 mL) is 90 mL;
in the fourth step, LiCl and 12-crown-4 are added into methanol, and then stirred for 0.5 to 2 hours at the stirring speed of 60 to 90 r/min;
the volume ratio of the mass of the azodiisobutyronitrile to the methanol in the step four (0.1 g-0.2 g) is 90 mL;
the volume ratio of the ethylene glycol dimethacrylate to the methanol in the step four (0.3 mL-0.7 mL) is 90 mL;
the volume ratio of the methacrylic acid to the methanol in the fourth step (0.3 mL-0.7 mL) is 90 mL.
2. The preparation method of the temperature response type bionic lithium ion imprinting composite membrane according to claim 1, characterized in that the volume ratio of the mass of the tris to the deionized water in the step one is (0.1 g-0.15 g) to 60 mL; the volume ratio of the mass of the dopamine hydrochloride to the deionized water in the step one (0.2 g-0.25 g) is 60 mL; the PVDF film in the first step has the diameter of 47mm and the thickness of 0.45 μm.
3. The method for preparing a temperature-responsive biomimetic lithium ion imprinted composite membrane according to claim 1, wherein the alkaline pH value in the first step is 8.5; the stirring speed in the step one is 30 r/min-60 r/min, and the stirring time is 6 h-8 h; in the first step, the PVDF membrane is washed for 3 to 5 times by using deionized water, and then dried for 1 to 2 hours at the temperature of between 50 and 70 ℃ to obtain the PDA @ PVDF membrane.
4. The preparation method of the temperature response type bionic lithium ion imprinting composite membrane according to claim 1, characterized in that in the second step, the reaction is carried out for 20 h-24 h under the conditions of nitrogen atmosphere, stirring speed of 60 r/min-90 r/min and ice bath, after the reaction is finished, the PVDF membrane is taken out, the PVDF membrane is alternately cleaned by deionized water and absolute ethyl alcohol for 3-5 times, and finally dried for 8 h-12 h at the temperature of 35 ℃ -45 ℃ to obtain the PDA @ PVDF-RAFT membrane.
5. The preparation method of the temperature response type bionic lithium ion imprinting composite membrane according to claim 1, characterized in that after the reaction is finished, the PVDF membrane is taken out, the PVDF membrane is alternately cleaned by deionized water and absolute ethyl alcohol for 3 to 5 times, and finally dried for 8 to 12 hours at the temperature of 35 to 45 ℃ to obtain the PDA @ PVDF-RAFT-PDEA membrane.
6. The preparation method of the temperature response type bionic lithium ion imprinting composite membrane according to claim 1, characterized in that in the fourth step, the PVDF membrane is taken out after the reaction is finished under the nitrogen atmosphere, the stirring speed is 30 r/min-60 r/min and the temperature is 75 ℃ for condensation reflux for 16 h-24 h, the PVDF membrane is alternately cleaned by deionized water and absolute ethyl alcohol for 3-5 times, and finally dried for 8 h-12 h at the temperature of 35 ℃ -45 ℃ to obtain Li-TSIIM, namely the temperature response type bionic lithium ion imprinting composite membrane.
7. The application of the temperature response type bionic lithium ion imprinting composite membrane prepared by the preparation method of claim 1, which is characterized in that the temperature response type bionic lithium ion imprinting composite membrane is used for absorbing Li+。
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