CN113351188A - Preparation method and application of bionic lithium ion imprinted membrane with catechol/chitosan as interface adhesion layer - Google Patents

Preparation method and application of bionic lithium ion imprinted membrane with catechol/chitosan as interface adhesion layer Download PDF

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CN113351188A
CN113351188A CN202110770251.8A CN202110770251A CN113351188A CN 113351188 A CN113351188 A CN 113351188A CN 202110770251 A CN202110770251 A CN 202110770251A CN 113351188 A CN113351188 A CN 113351188A
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membrane
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chitosan
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catechol
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CN113351188B (en
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李正
何广泽
姜虹
陈佳
郎若钦
姜毅鸣
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Electric Power Research Institute of State Grid Jilin Electric Power Co Ltd
Northeast Electric Power University
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Northeast Dianli University
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Abstract

A preparation method and application of a bionic lithium ion imprinted membrane with catechol/chitosan as an interface adhesion layer relate to a preparation method and application of a bionic lithium ion imprinted membrane. The invention aims to solve the problem of high cost of the conventional bionic ion imprinting adhesive layer. The method comprises the following steps: firstly, preparing a PVDF-CA/CS membrane; secondly, preparing a bionic lithium ion imprinted membrane with CA/CS as an interface adhesion layer; bionic lithium ion imprinted membrane using catechol/chitosan as interface adhesion layer and used for absorbing Li+. The bionic lithium ion imprinted membrane prepared by the invention has better selection on lithium ions by taking catechol/chitosan as an interface adhesion layerHas good adsorption capacity, strong regeneration and good chemical stability. The invention can obtain the bionic lithium ion imprinted membrane with catechol/chitosan as an interface adhesion layer.

Description

Preparation method and application of bionic lithium ion imprinted membrane with catechol/chitosan as interface adhesion layer
Technical Field
The invention relates to a preparation method and application of a bionic lithium ion imprinted membrane.
Background
Lithium, an important metal, has a great influence on the human society, and has been widely used in the production of lithium ion batteries in recent years. Lithium ion batteries are the most common rechargeable batteries in electronic products, including mobile phones, computers, electric vehicles, and the like. Although natural lithium resources are widely present in salt lake water as well as natural minerals, natural lithium resources are not sufficient to meet the global demand for lithium at the present consumption rate. Therefore, the rapid and efficient separation and recovery of lithium from waste lithium ion batteries has become the leading edge of research in the field.
At present, the common modes for separating and recovering lithium from waste lithium ion batteries mainly comprise a chemical method, an extraction method and a membrane separation method. Among them, the membrane separation method has been the focus of research in this field because of its good separation effect and low cost. However, membrane separation methods lack selectivity for the target ion, resulting in inefficient separation. In recent years, ion imprinting membranes are prepared by coupling ion imprinting technology and membrane separation technology, so that the membrane separation technology obtains a specific recognition effect on target ions. However, in the preparation process of the ion imprinting membrane, uniform active sites are difficult to form on the surface of the membrane, so that the ion imprinting layer is agglomerated, and the adsorption effect is reduced. This requires the search for suitable membrane modification means to impart uniform active sites to the membrane. The bionic dopamine contains a large amount of amino and phenolic hydroxyl groups, so that uniform active sites can be easily formed on the surface of the membrane, and the bionic dopamine is widely used as an interface adhesion layer of the ion imprinting membrane, and the phenomenon of agglomeration of the ion imprinting layer is avoided. However, the bionic dopamine is high in price, is not beneficial to further development of the field of ion imprinted membrane preparation, and limits the industrialization process of the ion imprinted membrane. Therefore, the search for an interface adhesion layer with low cost and good effect becomes the key to solve the technical bottleneck.
Disclosure of Invention
The invention aims to solve the problem of high cost of the existing bionic ion imprinting adhesion layer, and provides a preparation method and application of a bionic lithium ion imprinting film with catechol/chitosan as an interface adhesion layer.
A preparation method of a bionic lithium ion imprinted membrane with catechol/chitosan as an interface adhesion layer is completed according to the following steps:
firstly, preparing a PVDF-CA/CS membrane:
firstly, cleaning a PVDF membrane to obtain a cleaned PVDF membrane;
② immersing the cleaned PVDF membrane into NaAC solution, then adding NaIO4Stirring the solution, the chitosan solution and the catechol solution in a water bath kettle for reaction, taking out the PVDF membrane after the reaction is finished, washing the PVDF membrane with deionized water, and drying the PVDF membrane to obtain a PVDF-CA/CS membrane;
secondly, preparing a bionic lithium ion imprinted membrane with CA/CS as an interface adhesion layer:
firstly, adding LiCl and 12-crown-4 into acetonitrile, and stirring to obtain a mixed solution;
immersing the PVDF-CA/CS membrane into the mixed solution, adding azodiisobutyronitrile, ethylene glycol dimethacrylate and methacrylic acid, introducing nitrogen, sealing the reaction system, performing condensation reflux at 75 ℃ under the nitrogen atmosphere and under stirring, taking out and cleaning the PVDF membrane after the reaction is finished, cleaning the PVDF membrane by using hydrochloric acid, and removing Li+And finally drying to obtain the CA/CS-LIIM membrane, namely the bionic lithium ion imprinted membrane taking catechol/chitosan as an interface adhesion layer.
Bionic lithium ion imprinted membrane using catechol/chitosan as interface adhesion layer and used for absorbing Li+。
The principle of the invention is as follows:
firstly, the bionic dopamine contains a large amount of phenolic hydroxyl and amino, and Catechol (CA) and Chitosan (CS) can respectively provide phenolic hydroxyl and amino, so that the substitution effect of the bionic dopamine is realized;
secondly, chitosan is the second largest natural polymer with the second storage amount to cellulose, the biosynthesis amount of the chitosan is about 100 hundred million tons every year, and the chitosan is a recyclable renewable resource and inexhaustible; catechol generally refers to catechol, and is widely found in nature, particularly in plants, mostly in the form of derivatives. Both of which conform to biomimetic localization;
and thirdly, catechol and chitosan can respectively provide phenolic hydroxyl and amino for the interface adhesion layer, but the price is far lower than that of bionic dopamine, so that the function of replacing the interface adhesion layer is achieved.
Static adsorption experiment:
adding a certain amount of CA/CS-LIIM film into the corresponding test solution, oscillating in a constant-temperature water bath at the temperature of 25 ℃, and inspecting different Li+CA/CS-LIIM film vs Li at initial concentration+The adsorption capacity of (1). 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)。
Figure BDA0003152325670000021
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 CA/CS-LIIM membrane added, and V (mL) is the volume of the test solution.
Selective adsorption experiments:
adding Li into a certain amount of CA/CS-LIIM film+And Co2+In the mixed solution of (1), shaking in a constant-temperature water bath at a temperature of 25 ℃ for a certain time, and examining Co2+Under the interference of (2), the CA/CS-LIIM film is opposite to Li+Selective adsorption performance of. Testing of CA/CS-LIIM film vs Li+And Co2+The method of adsorption capacity is the same as the static adsorption experiment.
The invention has the beneficial effects that:
1. the catechol/chitosan is taken as an interface adhesion layer, so that the effect similar to that of bionic dopamine can be achieved, and a large amount of phenolic hydroxyl and amino are provided, so that uniform active sites on the surface of the membrane can be provided, and the ion imprinting layer can be further conveniently loaded;
2. catechol and chitosan are substances from nature, and have huge yield, inexhaustible amount, so the cost is far lower than that of bionic dopamine;
3. the bionic lithium ion imprinted membrane prepared by the invention has good selective adsorption capacity on lithium ions, and has the characteristics of strong reproducibility and good chemical stability.
The invention can obtain the bionic lithium ion imprinted membrane with catechol/chitosan as an interface adhesion layer.
Drawings
FIG. 1 is a flow chart of example 1 for preparing a biomimetic lithium ion imprinted membrane with catechol/chitosan as an interface adhesion layer;
FIG. 2 is an infrared spectrum in which 1 is a PVDF membrane, 2 is a PVDF-CA/CS membrane prepared in the first step of example 1, and 3 is a CA/CS-LIIM membrane prepared in the second step of example 1;
FIG. 3 is a SEM image showing a PVDF membrane as a component a, a PVDF-CA/CS membrane as a component b prepared in the first step of example 1, and a CA/CS-LIIM membrane as a component c prepared in the second step of example 1.
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 preparation method of the bionic lithium ion imprinted membrane with catechol/chitosan as the interface adhesion layer in the embodiment is completed according to the following steps:
firstly, preparing a PVDF-CA/CS membrane:
firstly, cleaning a PVDF membrane to obtain a cleaned PVDF membrane;
② cleaning the wastePVDF membrane is immersed in NaAC solution, then NaIO is added4Stirring the solution, the chitosan solution and the catechol solution in a water bath kettle for reaction, taking out the PVDF membrane after the reaction is finished, washing the PVDF membrane with deionized water, and drying the PVDF membrane to obtain a PVDF-CA/CS membrane;
secondly, preparing a bionic lithium ion imprinted membrane with CA/CS as an interface adhesion layer:
firstly, adding LiCl and 12-crown-4 into acetonitrile, and stirring to obtain a mixed solution;
immersing the PVDF-CA/CS membrane into the mixed solution, adding azodiisobutyronitrile, ethylene glycol dimethacrylate and methacrylic acid, introducing nitrogen, sealing the reaction system, performing condensation reflux at 75 ℃ under the nitrogen atmosphere and under stirring, taking out and cleaning the PVDF membrane after the reaction is finished, cleaning the PVDF membrane by using hydrochloric acid, and removing Li+And finally drying to obtain the CA/CS-LIIM membrane, namely the bionic lithium ion imprinted membrane taking catechol/chitosan as an interface adhesion layer.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the diameter of the PVDF film in the first step is 47mm, and the thickness is 0.45 μm; firstly, washing the PVDF membrane for 3-5 times by using deionized water, and then washing the PVDF membrane for 3-5 times by using absolute ethyl alcohol to obtain the cleaned PVDF membrane. 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 concentration of the NaAC solution in the first step is 50 mmol/L-70 mmol/L, and NaIO4The concentration of the solution is 20 mmol/L-30 mmol/L, the concentration of the chitosan solution is 10 g/L-20 g/L, and the concentration of the catechol solution is 1 g/L-2 g/L. 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 NaAC solution and NaIO in the step one4The volume ratio of the solution is 100 (10-30); the volume ratio of the NaAC solution to the chitosan solution in the first step is 100 (10-30); step one, the NaAC solution andthe volume ratio of the catechol solution is 100 (10-30). 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: the preparation method of the NaAC solution in the first step is as follows: adding sodium acetate trihydrate into deionized water, adjusting the pH value of the solution to 5 by using 0.1mol/L hydrochloric acid after dissolving to obtain a NaAC solution with the pH value of 5 and the concentration of 50 mmol/L-70 mmol/L; NaIO described in step one4The preparation method of the solution is as follows: sodium periodate is added into deionized water and dissolved to obtain NaIO with the concentration of 20mmol/L to 30mmol/L4A solution; the preparation method of the chitosan solution in the first step is as follows: adding chitosan into an acetic acid solution with the volume fraction of 1%, and stirring for 20-24 h to obtain a chitosan solution with the concentration of 10-20 g/L; the concentration of the chitosan is less than 200mPa & s. 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: the drying temperature in the first step is 65-75 ℃, and the drying time is 1-5 h; step one, immersing the cleaned PVDF membrane into NaAC solution, and then adding NaIO4The solution, the chitosan solution and the catechol solution are stirred and reacted for 1 to 2 hours in a water bath kettle at the temperature of between 30 and 35 ℃, and the stirring speed is between 30 and 60 r/min. 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: the volume ratio of the LiCl to the acetonitrile in the second step is (0.3 g-0.5 g) 90 mL; the volume ratio of the 12-crown ether-4 to the acetonitrile in the second step is (0.3-0.5): 90; the stirring time in the second step is 0.15-2 h. 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 mass of the azodiisobutyronitrile in the second step to the acetonitrile in the second step (0.1 g-0.2 g) is 90 mL; the volume ratio of the ethylene glycol dimethacrylate in the second step to the acetonitrile in the second step is (0.3-0.7 mL):90 mL; the volume ratio of the methacrylic acid in the second step to the acetonitrile in the second step is (0.3 mL-0.7 mL):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: in the second step, the PVDF membrane is taken out after the reaction is finished, the PVDF membrane is alternately cleaned by deionized water and absolute ethyl alcohol for 3 to 5 times after the condensation reflux is carried out for 16 to 24 hours under the nitrogen atmosphere at the stirring speed of 30 to 60r/min and at the temperature of 75 ℃, and then the PVDF membrane is cleaned by hydrochloric acid with the concentration of 1mol/L to remove Li+And finally drying at 45-50 ℃ for 1-2 h to obtain CA/CS-LIIM, namely the bionic lithium ion imprinted membrane taking catechol/chitosan as an interface adhesion layer. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: in the embodiment, the bionic lithium ion imprinted membrane using catechol/chitosan as the interface adhesion layer is used for absorbing Li+。
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Example 1: a preparation method of a bionic lithium ion imprinted membrane with catechol/chitosan as an interface adhesion layer is completed according to the following steps:
firstly, preparing a PVDF-CA/CS membrane:
firstly, washing the PVDF membrane for 3 times by using deionized water, and then washing the PVDF membrane for 3 times by using absolute ethyl alcohol to obtain a washed PVDF membrane;
the diameter of the PVDF film in the first step is 47mm, and the thickness is 0.45 μm;
② immersing the cleaned PVDF membrane into 100mL NaAC solution with concentration of 50mmol/L, then adding 20mL NaIO with concentration of 20mmol/L4The solution, 10mL of chitosan solution with the concentration of 10g/L and 25mL of catechol solution with the concentration of 1g/L are stirred and reacted for 1h in a water bath kettle with the temperature of 30 ℃ at the stirring speed of 30r/min,after the reaction is finished, taking out the PVDF membrane, washing the PVDF membrane by using deionized water, and drying the PVDF membrane for 1h at 65 ℃ to obtain a PVDF-CA/CS membrane;
the preparation method of the NaAC solution in the first step is as follows: adding sodium acetate trihydrate into deionized water, and adjusting the pH value of the solution to 5 by using 0.1mol/L hydrochloric acid after dissolving to obtain a NaAC solution with the pH value of 5 and the concentration of 50 mmol/L; NaIO described in step one4The preparation method of the solution is as follows: adding sodium periodate into deionized water, and dissolving to obtain NaIO with concentration of 20mmol/L4A solution; the preparation method of the chitosan solution in the first step is as follows: adding chitosan into an acetic acid solution with the volume fraction of 1%, and stirring for 20-24 h to obtain a chitosan solution with the concentration of 10 g/L; the concentration of the chitosan is less than 200mPa & s;
secondly, preparing a bionic lithium ion imprinted membrane with CA/CS as an interface adhesion layer:
adding 0.3g of LiCl and 0.3mL of 12-crown ether-4 into 90mL of acetonitrile, and stirring for 2 hours at the stirring speed of 30r/min to obtain a mixed solution;
immersing the PVDF-CA/CS membrane into the mixed solution, adding 0.1g of azobisisobutyronitrile, 0.3mL of ethylene glycol dimethacrylate and 0.3mL of methacrylic acid, introducing nitrogen for 30min, sealing the reaction system, carrying out condensation reflux for 16h under the nitrogen atmosphere at the stirring speed of 30r/min and the temperature of 75 ℃, taking out the PVDF membrane for cleaning after the reaction is finished, cleaning the PVDF membrane by using 1mol/L hydrochloric acid, and removing Li+And finally drying for 1h at 50 ℃ to obtain a CA/CS-LIIM membrane, namely the bionic lithium ion imprinted membrane taking catechol/chitosan as an interface adhesion layer.
FIG. 1 is a flow chart of example 1 for preparing a biomimetic lithium ion imprinted membrane with catechol/chitosan as an interface adhesion layer;
FIG. 2 is an infrared spectrum in which 1 is a PVDF membrane, 2 is a PVDF-CA/CS membrane prepared in the first step of example 1, and 3 is a CA/CS-LIIM membrane prepared in the second step of example 1;
curve 2 is 1540cm in comparison with curve 1-1And 1645cm-1New absorption peak componentOther reasons are N-H bending vibration and C ═ C resonance vibration of the aromatic ring. 3000-3700 cm-1The new broad absorption peaks at (A) are due to-OH and-NH2Stretching vibrations of (a), these groups being derived from chitosan and catechol, respectively; this demonstrates the successful fabrication of PVDF-CA/CS membranes; curve 3 is 1543cm in comparison with curve 2-1、1231cm-1、1173cm-1And 1424cm-1The new characteristic peaks appeared in the compound are respectively due to C ═ O stretching vibration, C-O bending vibration, C-O stretching vibration and CH of 12-crown-42Bending vibration; these new characteristic peaks appeared to demonstrate the successful loading of 12-crown-4 on the surface of PVDF-CA/CS membrane, resulting in CA/CS-LIIM membrane.
FIG. 3 is a SEM photograph showing a PVDF membrane as a component a, a PVDF-CA/CS membrane as a component b prepared in the first step of example 1, and a CA/CS-LIIM membrane as a component c prepared in the second step of example 1;
by comparing b with a, the surface of b is increased by some particulate matter due to successful loading of chitosan particles; and the surface roughness of c is obviously enhanced by comparing c with a and b, which indicates that the 12-crown-4 is successfully loaded, and the CA/CS-LIIM film is successfully prepared.
Static adsorption experiment: 6 parts of the CA/CS-LIIM film 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 3h at the temperature of 25 ℃. 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+When the concentration is 200mg/L, the adsorption capacity of the CA/CS-LIIM membrane is the maximum, and the highest saturated adsorption capacity is 56.85 mg/g.
Selective adsorption experiments: 0.1g of the CA/CS-LIIM film prepared in example 1 was added to 100mL of a solution containing Li+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+Under the interference of (2), the CA/CS-LIIM film is opposite to Li+Selective adsorption performance of.
The results show that the CA/CS-LIIM film prepared in example 1 was aligned with Li in the mixed solution+Has an adsorption capacity of 40.58mg/g for Co2+The adsorption capacity of (A) was 11.2mg/g, which proved that the CA/CS-LIIM film was resistant to Li+Has high selectivity.
The embodiment 2 is different from the embodiment 1 in that: in the second step, 0.4g LiCl and 0.4mL 12-crown-4 were added to 90mL acetonitrile, and the mixture was stirred at 30r/min for 2 hours to obtain a mixed solution. The other steps and parameters were the same as in example 1.
Selective adsorption experiments: 0.1g of the CA/CS-LIIM film prepared in example 2 was added to 100mL of a solution containing Li+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+Under the interference of (2), the CA/CS-LIIM film is opposite to Li+Selective adsorption performance of.
The results show that the CA/CS-LIIM film prepared in example 2 was aligned to Li in the mixed solution+Has an adsorption capacity of 48.6mg/g for Co2+The adsorption capacity of (A) was 13.1mg/g, which proved that the CA/CS-LIIM film was resistant to Li+Has high selectivity.
The embodiment 3 is different from the embodiment 1 in that: in the second step, 0.5g LiCl and 0.5mL 12-crown-4 were added to 90mL acetonitrile, and the mixture was stirred at 30r/min for 2 hours to obtain a mixed solution. The other steps and parameters were the same as in example 1.
Selective adsorption experiments: 0.1g of the CA/CS-LIIM film prepared in example 3 was added to 100mL of a solution containing Li+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+Under the interference of (2), the CA/CS-LIIM film is opposite to Li+Selective adsorption performance of.
The results show that the CA/CS-LIIM film prepared in example 3 was aligned to Li in the mixed solution+Has an adsorption capacity of 38.26mg/g for Co2+The adsorption capacity of the film was 7.58mg/g, which proved that the CA/CS-LIIM film was resistant to Li+Has high selectivity.
CA/CS-LIIM film prepared in example 3 vs Li+And Co2+The reason for the decrease in the adsorption capacity is that the adsorption amount is decreased by the phenomenon that the recognition site (12-crown-4) is embedded due to the excessive amount of 12-crown-4 added.

Claims (10)

1. A preparation method of a bionic lithium ion imprinted membrane with catechol/chitosan as an interface adhesion layer is characterized by comprising the following steps:
firstly, preparing a PVDF-CA/CS membrane:
firstly, cleaning a PVDF membrane to obtain a cleaned PVDF membrane;
② immersing the cleaned PVDF membrane into NaAC solution, then adding NaIO4Stirring the solution, the chitosan solution and the catechol solution in a water bath kettle for reaction, taking out the PVDF membrane after the reaction is finished, washing the PVDF membrane with deionized water, and drying the PVDF membrane to obtain a PVDF-CA/CS membrane;
secondly, preparing a bionic lithium ion imprinted membrane with CA/CS as an interface adhesion layer:
firstly, adding LiCl and 12-crown-4 into acetonitrile, and stirring to obtain a mixed solution;
immersing the PVDF-CA/CS membrane into the mixed solution, adding azodiisobutyronitrile, ethylene glycol dimethacrylate and methacrylic acid, introducing nitrogen, sealing the reaction system, performing condensation reflux at 75 ℃ under the nitrogen atmosphere and under stirring, taking out and cleaning the PVDF membrane after the reaction is finished, cleaning the PVDF membrane by using hydrochloric acid, and removing Li+And finally drying to obtain the CA/CS-LIIM membrane, namely the bionic lithium ion imprinted membrane taking catechol/chitosan as an interface adhesion layer.
2. The preparation method of the bionic lithium ion imprinted membrane with catechol/chitosan as the interface adhesion layer according to claim 1, wherein the PVDF membrane in the first step has a diameter of 47mm and a thickness of 0.45 μm; firstly, washing the PVDF membrane for 3-5 times by using deionized water, and then washing the PVDF membrane for 3-5 times by using absolute ethyl alcohol to obtain the cleaned PVDF membrane.
3. The method for preparing a bionic lithium ion imprinted membrane with catechol/chitosan as an interface adhesion layer according to claim 1, wherein the concentration of NaAC solution in the first step is 50-70 mmol/L, and NaIO4The concentration of the solution is 20 mmol/L-30 mmol/L, the concentration of the chitosan solution is 10 g/L-20 g/L, and the concentration of the catechol solution is 1 g/L-2 g/L.
4. The method for preparing a bionic lithium ion imprinted membrane with catechol/chitosan as an interface adhesion layer according to claim 1 or 3, wherein the NaAC solution and NaIO are in the first step4The volume ratio of the solution is 100 (10-30); the volume ratio of the NaAC solution to the chitosan solution in the first step is 100 (10-30); the volume ratio of the NaAC solution to the catechol solution in the first step is 100 (10-30).
5. The method for preparing a bionic lithium ion imprinted membrane with catechol/chitosan as an interface adhesive layer according to claim 4, wherein the NaAC solution is prepared by the following steps: adding sodium acetate trihydrate into deionized water, adjusting the pH value of the solution to 5 by using 0.1mol/L hydrochloric acid after dissolving to obtain a NaAC solution with the pH value of 5 and the concentration of 50 mmol/L-70 mmol/L; NaIO described in step one4The preparation method of the solution is as follows: sodium periodate is added into deionized water and dissolved to obtain NaIO with the concentration of 20mmol/L to 30mmol/L4A solution; the preparation method of the chitosan solution in the first step is as follows: adding chitosan into an acetic acid solution with the volume fraction of 1%, and stirring for 20-24 h to obtain a chitosan solution with the concentration of 10-20 g/L; the concentration of the chitosan is less than 200mPa & s.
6. The method for preparing a bionic lithium ion imprinted membrane with catechol/chitosan as interface adhesive layer according to claim 1, wherein the bionic lithium ion imprinted membrane is prepared by the methodThe drying temperature in the first step is 65-75 ℃, and the drying time is 1-5 h; step one, immersing the cleaned PVDF membrane into NaAC solution, and then adding NaIO4The solution, the chitosan solution and the catechol solution are stirred and reacted for 1 to 2 hours in a water bath kettle at the temperature of between 30 and 35 ℃, and the stirring speed is between 30 and 60 r/min.
7. The preparation method of the bionic lithium ion imprinted membrane with catechol/chitosan as the interface adhesion layer according to claim 1, wherein the volume ratio of LiCl to acetonitrile in the second step is (0.3 g-0.5 g):90 mL; the volume ratio of the 12-crown ether-4 to the acetonitrile in the second step is (0.3-0.5): 90; the stirring time in the second step is 0.15-2 h.
8. The preparation method of the bionic lithium ion imprinted membrane with catechol/chitosan as the interface adhesion layer according to claim 1, wherein the volume ratio of the mass of azodiisobutyronitrile in the second step to the volume of acetonitrile in the second step (i) is (0.1 g-0.2 g):90 mL; the volume ratio of the ethylene glycol dimethacrylate in the second step to the acetonitrile in the second step is (0.3-0.7 mL):90 mL; the volume ratio of the methacrylic acid in the second step to the acetonitrile in the second step is (0.3 mL-0.7 mL):90 mL.
9. The method for preparing a bionic lithium ion imprinted membrane with catechol/chitosan as an interface adhesion layer according to claim 1, wherein in the second step, the condensation reflux is carried out for 16h to 24h under the nitrogen atmosphere, the stirring speed is 30r/min to 60r/min and the temperature is 75 ℃, after the reaction is finished, the PVDF membrane is taken out, deionized water and absolute ethyl alcohol are used for alternately cleaning the PVDF membrane for 3 to 5 times, hydrochloric acid with the concentration of 1mol/L is used for cleaning the PVDF membrane, and Li is removed+And finally drying at 45-50 ℃ for 1-2 h to obtain CA/CS-LIIM, namely the bionic lithium ion imprinted membrane taking catechol/chitosan as an interface adhesion layer.
10. The application of the bionic lithium ion imprinted membrane prepared by the preparation method of claim 1 and taking catechol/chitosan as the interface adhesion layer, which is characterized in that the bionic lithium ion imprinted membrane taking catechol/chitosan as the interface adhesion layer is used for absorbing Li+。
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