CN114984926A - A kind of preparation method of high anti-agglomeration RGO-based magnetic lithium ion imprinted polymer - Google Patents

Abstract

A preparation method of a high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer relates to a preparation method of a lithium ion imprinted polymer. The invention aims to solve the problems that the existing method for recovering lithium is high in cost and complicated in steps, and the existing method for preparing the magnetic ion imprinted polymer is responsible for and easy to agglomerate, so that the adsorption capacity of lithium is reduced. The method comprises the following steps: firstly, preparation of Fe ₃ O ₄ /RGO; II, preparing Fe ₃ O ₄ @SiO ₂ And @ IIP/RGO, namely the high agglomeration resistant RGO-based magnetic lithium ion imprinted polymer. Compared with the existing lithium ion imprinted material, the high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer prepared by the invention has obvious agglomeration resistance, and the saturated adsorption capacity is remarkably improved. The high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer prepared by the invention is used for lithiumThe adsorption rate of the ions can reach 99.9%. The invention can obtain the high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer.

Description

A kind of preparation method of high anti-agglomeration RGO-based magnetic lithium ion imprinted polymer

technical field

The invention relates to a preparation method of a lithium ion imprinted polymer.

Background technique

Lithium-ion batteries have the advantages of long service life, high energy storage density, and strong high and low temperature adaptability, and are widely used in new energy vehicles and various portable electronic products. In 2021, the global consumption of lithium will reach 900,000 tons, and this number has a trend of increasing year by year. At present, the source of lithium mainly comes from lithium ore, but my country's lithium ore resources are limited, but salt lake resources are abundant. Therefore, lithium extraction from salt lake water has become a hot topic of resource conservation in recent years. The existing recycling technologies are mainly electrochemical deposition and chemical deposition, but such methods have high recycling costs and complicated steps. As an emerging technology in the field of separation and purification, ion blotting technology has been widely studied in recent years for its unique characteristics of high efficiency and good selective separation effect. Magnetic ion-imprinted polymers combine the advantages of ion-imprinting technology and magnetic separation technology, reflecting the characteristics of economy, high efficiency, and easy industrialization. However, the agglomeration of nanoparticulate polymers, resulting in reduced adsorption capacity and complicated preparation process, are the main reasons hindering the further development of this technology.

SUMMARY OF THE INVENTION

The purpose of the present invention is to solve the problem that the existing method for recovering lithium has high cost and complicated steps, and the existing magnetic ion imprinted polymer preparation method is responsible and easy to agglomerate, resulting in the reduction of lithium adsorption capacity, and provides a high anti-agglomeration RGO Preparation method of base magnetic lithium ion imprinted polymer.

A preparation method of a high-anti-agglomeration RGO-based magnetic lithium ion imprinted polymer is completed according to the following steps:

1. First, dissolve the reduced graphene oxide in deionized water, then add FeSO ₄ ·7H ₂ O and FeCl ₃ ·6H ₂ O, and then add NaOH dropwise under the conditions of shaking in a water bath in a shaker and passing nitrogen into the solution solution, adjust the pH of the system, and finally shake the reaction in a water bath in a shaker under the protection of nitrogen atmosphere, the reaction is completed, and the reaction product I is obtained; the reaction product is washed and then dried to obtain Fe ₃ O ₄ /RGO;

2. Preparation of Fe ₃ O ₄ @SiO ₂ @IIP/RGO:

①, first add 1-aza-12-crown 4-ether, anhydrous lithium chloride, 3-aminopropyl triethoxysilane, ethyl orthosilicate and Fe ₃ O ₄ /RGO to absolute ethanol , stir evenly, then add a mixture of deionized water/ammonia water, and shake the reaction in a water bath to obtain reaction product II;

②. First, use absolute ethanol to clean the reaction product II, then use deionized water to clean the reaction product II, and then use hydrochloric acid to clean the reaction product II until no Li ⁺ can be detected by ICP-AES, and then use deionized water to clean the reaction product II. The reaction product II was washed with ionized water, and finally dried in vacuum to obtain Fe ₃ O ₄ @SiO ₂ @IIP/RGO, which is an RGO-based magnetic lithium ion imprinted polymer with high anti-agglomeration.

In the present invention, reduced graphene oxide (RGO) is used as a skeleton material, Fe ₃ O ₄ is embedded on its surface, combined with the modification method of magnetic nanoparticles wrapped by SiO ₂ , and 1-aza- 12-crown 4-ether, and finally through a one-step surface imprinting polymerization process to prepare RGO-based magnetic lithium ion imprinted polymer with high anti-agglomeration, which has good application prospects.

The advantages of the present invention are:

1. Compared with the current lithium ion imprinted materials, the high anti-agglomeration RGO-based magnetic lithium ion imprinted polymer prepared by the present invention has obvious anti-agglomeration properties, and the saturated adsorption capacity is significantly improved;

2. The high-anti-agglomeration RGO-based magnetic lithium ion imprinted polymer prepared by the present invention has the advantages of simple preparation method, sensitive adsorption, energy saving compared with other selective recovery methods, and good circulation effect;

3. Aiming at the complex environment in the acid leaching solution of waste lithium batteries, the present invention introduces magnetic material into the polymer to facilitate the magnetic separation and recovery of the polymer after working;

Fourth, the high anti-agglomeration RGO-based magnetic lithium ion imprinted polymer prepared by the invention has an adsorption rate of 99.9% to lithium ions.

The invention can obtain a high anti-aggregation RGO-based magnetic lithium ion imprinted polymer.

Description of drawings

Fig. 1 is the SEM image of the high anti-agglomeration RGO-based magnetic lithium ion imprinted polymer prepared in Example 1;

Fig. 2 is the SEM image of the high anti-agglomeration RGO-based magnetic lithium ion imprinted polymer prepared in Example 1;

FIG. 3 is a SEM image of the high-anti-agglomeration RGO-based magnetic lithium ion imprinted polymer prepared in Example 1. FIG.

Detailed ways

The following examples further illustrate the content of the present invention, but should not be construed as limiting the present invention. Modifications and substitutions made to the methods, steps or conditions of the present invention without departing from the essence of the present invention all belong to the scope of the present invention.

Embodiment 1: In this embodiment, a method for preparing a high-anti-agglomeration RGO-based magnetic lithium ion imprinted polymer is specifically completed according to the following steps:

1. First, dissolve the reduced graphene oxide in deionized water, then add FeSO ₄ ·7H ₂ O and FeCl ₃ ·6H ₂ O, and then add NaOH dropwise under the conditions of shaking in a water bath in a shaker and passing nitrogen into the solution solution, adjust the pH of the system, and finally shake the reaction in a water bath in a shaker under the protection of nitrogen atmosphere, the reaction is completed, and the reaction product I is obtained; the reaction product is washed and then dried to obtain Fe ₃ O ₄ /RGO;

2. Preparation of Fe ₃ O ₄ @SiO ₂ @IIP/RGO:

①, first add 1-aza-12-crown 4-ether, anhydrous lithium chloride, 3-aminopropyl triethoxysilane, ethyl orthosilicate and Fe ₃ O ₄ /RGO to absolute ethanol , stir evenly, then add a mixture of deionized water/ammonia water, and shake the reaction in a water bath to obtain reaction product II;

②. First, use absolute ethanol to clean the reaction product II, then use deionized water to clean the reaction product II, and then use hydrochloric acid to clean the reaction product II until no Li ⁺ can be detected by ICP-AES, and then use deionized water to clean the reaction product II. The reaction product II was washed with ionized water, and finally dried in vacuum to obtain Fe ₃ O ₄ @SiO ₂ @IIP/RGO, which is an RGO-based magnetic lithium ion imprinted polymer with high anti-agglomeration.

Embodiment 2: The difference between this embodiment and Embodiment 1 is: the mass ratio of the reduced graphene oxide described in step 1 to the volume of deionized water is (0.33g～3g): (60mL～200mL); The mass ratio of FeSO ₄ ·7H ₂ O described in step 1 to the volume of deionized water is (1.2g～3.6g):(60mL～200mL); the mass of FeCl ₃ ·6H ₂ O described in step 1 The volume ratio with deionized water is (2.33g～6.99g):(60mL～200mL). Other steps are the same as in the first embodiment.

Embodiment 3: The difference between this embodiment and Embodiment 1 or 2 is that: in step 1, the number of revolutions of the shaking table gyratory stirring is 60r/min～120r/min, and the temperature of the water bath is 60℃～80℃; The reaction time in step 1 is 1h～2h. Other steps are the same as in the first or second embodiment.

Embodiment 4: This embodiment differs from Embodiments 1 to 3 in that: the pH value of the adjustment system in step 1 is 8 to 10; the drying temperature in step 1 is 30°C to 50°C; The concentration of the NaOH solution is 1 mol/L. Other steps are the same as those of the specific embodiments 1 to 3.

Embodiment 5: This embodiment differs from Embodiments 1 to 4 in that: the temperature of the water bath in step 2 (1) is 25°C to 30°C, and the reaction time is 6h to 8h. The other steps are the same as those in the first to fourth embodiments.

Embodiment 6: This embodiment differs from Embodiments 1 to 5 in that: 1-aza-12-crown 4-ether, 3-aminopropyltriethoxysilane, 1-aza-12-crown 4-ether, 3-aminopropyltriethoxysilane, The volume ratio of the mixture of ethyl orthosilicate, anhydrous ethanol and deionized water/ammonia is (0.3mL~0.9mL):(2mL~6mL):(8mL~24mL):(20mL~60mL):(30mL ~90mL). Other steps are the same as those of the specific embodiments 1 to 5.

Embodiment 7: The difference between this embodiment and Embodiments 1 to 6 is that the mass ratio of the anhydrous lithium chloride and Fe ₃ O ₄ /RGO described in step 2 ① is (1.29g～3.87g) : (1.33g～4g). Other steps are the same as those of the specific embodiments 1 to 6.

Embodiment 8: The difference between this embodiment and Embodiments 1 to 7 is: the mass ratio of the anhydrous lithium chloride described in step 2 ① to the volume ratio of 1-aza-12-crown 4-ether is (1.29g～3.8g): (0.3mL～0.9mL). Other steps are the same as those of the specific embodiments 1 to 7.

Embodiment 9: The difference between this embodiment and Embodiments 1 to 8 is: the volume ratio of deionized water and ammonia in the mixed solution of deionized water/ammonia described in step 2 ① is 2:1, wherein The mass fraction of ammonia water is 25% to 30%. Other steps are the same as those of the specific embodiments 1 to 8.

Embodiment 10: The difference between this embodiment and Embodiments 1 to 9 is that the temperature of vacuum drying in step 2 (2) is 50°C to 60°C; Wash 3 to 5 times, then use deionized water to wash reaction product II for 3 to 5 times, and then use hydrochloric acid with a mass fraction of 35% to 40% to wash reaction product II until it cannot be detected by ICP-AES Then, the reaction product II was washed with deionized water until the pH value was 7, and finally vacuum-dried to obtain Fe ₃ O ₄ @SiO ₂ @IIP/RGO, which is a high-anti-agglomeration RGO-based magnetic lithium ^ion imprinted polymerization thing. Other steps are the same as those of the specific embodiments 1 to 9.

Adopt the following examples to verify the beneficial effects of the present invention:

Embodiment 1: a kind of preparation method of high anti-agglomeration RGO-based magnetic lithium ion imprinted polymer, it is characterized in that this preparation method is specifically completed according to the following steps:

1. First dissolve 1g of reduced graphene oxide in 66.37mL of deionized water, then add 1.20g FeSO ₄ ·7H ₂ O and 2.33g FeCl ₃ ·6H ₂ O, then shake in a water bath at 80°C in a shaker and pass through the solution 33.63 mL of NaOH solution with a concentration of 1 mol/L was added dropwise under the condition of nitrogen gas, and finally, under the protection of nitrogen atmosphere, the reaction was shaken in a water bath for 1 h in a shaking table, the reaction was completed, and the reaction product I was obtained; the reaction product was rinsed with deionized water for 6 and then vacuum-dried at 50 °C to obtain Fe ₃ O ₄ /RGO;

In step 1, the number of revolutions of the shaking table gyratory stirring is 60r/min;

2. Preparation of Fe ₃ O ₄ @SiO ₂ @IIP/RGO:

①, at first 0.3mL 1-aza-12-crown 4-ether, 1.29g anhydrous lithium chloride, 2mL 3-aminopropyl triethoxysilane, 8mL tetraethyl orthosilicate and the Fe obtained in step one ₃ O ₄ /RGO was added to 20 mL of anhydrous ethanol, stirred evenly, then 30 mL of deionized water/ammonia mixture was added, and the reaction was carried out in a water bath at 25 °C for 8 h to obtain reaction product II;

The volume ratio of deionized water and ammonia water in the mixed solution of deionized water/ammonia water described in step 2 1. is 2:1, and wherein the mass fraction of ammonia water is 25%;

②. First, use anhydrous ethanol to wash the reaction product II for 5 times, then use deionized water to wash the reaction product II for 3 to 5 times, and then use 35% hydrochloric acid to wash the reaction product II until ICP-AES can not detect Li ⁺ , then use deionized water to wash the reaction product II to pH 7, and finally vacuum dry at 50 °C to obtain Fe ₃ O ₄ @SiO ₂ @IIP/RGO, which is High anti-agglomeration RGO-based magnetic lithium-ion imprinted polymer.

Embodiment 2: a kind of preparation method of high anti-agglomeration RGO-based magnetic lithium ion imprinted polymer, it is characterized in that this preparation method is specifically completed according to the following steps:

1. First dissolve 0.33g of reduced graphene oxide in 66.37mL of deionized water, then add 1.20g FeSO ₄ ·7H ₂ O and 2.33g FeCl ₃ ·6H ₂ O, and then shake in a water bath at 80°C in a shaker and add to the solution 33.63 mL of NaOH solution with a concentration of 1 mol/L was added dropwise under the condition of introducing nitrogen, and finally, under the protection of nitrogen atmosphere, the reaction was shaken in a water bath for 1 h in a shaking table, the reaction was completed, and the reaction product I was obtained; the reaction product was rinsed with deionized water. 6 times, and then vacuum-dried at 50 °C to obtain Fe ₃ O ₄ /RGO;

In step 1, the number of revolutions of the shaking table gyratory stirring is 60r/min;

2. Preparation of Fe ₃ O ₄ @SiO ₂ @IIP/RGO:

①, at first 0.3mL 1-aza-12-crown 4-ether, 1.29g anhydrous lithium chloride, 2mL 3-aminopropyl triethoxysilane, 8mL tetraethyl orthosilicate and the Fe obtained in step one ₃ O ₄ /RGO was added to 20 mL of anhydrous ethanol, stirred evenly, then 30 mL of deionized water/ammonia mixture was added, and the reaction was carried out in a water bath at 25 °C for 8 h to obtain reaction product II;

The volume ratio of deionized water and ammonia water in the mixed solution of deionized water/ammonia water described in step 2 1. is 2:1, and wherein the mass fraction of ammonia water is 28%;

②. First, use anhydrous ethanol to wash the reaction product II for 5 times, then use deionized water to wash the reaction product II for 3 to 5 times, and then use 35% hydrochloric acid to wash the reaction product II until ICP-AES can not detect Li ⁺ , then use deionized water to wash the reaction product II to pH 7, and finally vacuum dry at 50 °C to obtain Fe ₃ O ₄ @SiO ₂ @IIP/RGO, which is High anti-agglomeration RGO-based magnetic lithium-ion imprinted polymer.

Embodiment 3: a kind of preparation method of high anti-agglomeration RGO-based magnetic lithium ion imprinted polymer, it is characterized in that this preparation method is specifically completed according to the following steps:

1. First dissolve 3g of reduced graphene oxide in 66.37mL of deionized water, then add 1.20g FeSO ₄ ·7H ₂ O and 2.33g FeCl ₃ ·6H ₂ O, then shake in a water bath at 80°C in a shaker and pass through the solution 33.63 mL of NaOH solution with a concentration of 1 mol/L was added dropwise under the condition of nitrogen gas, and finally, under the protection of nitrogen atmosphere, the reaction was shaken in a water bath for 1 h in a shaking table, the reaction was completed, and the reaction product I was obtained; the reaction product was rinsed with deionized water for 6 times, and then vacuum-dried at 50 °C to obtain Fe ₃ O ₄ /RGO;

In step 1, the number of revolutions of the shaking table gyratory stirring is 60r/min;

2. Preparation of Fe ₃ O ₄ @SiO ₂ @IIP/RGO:

①, at first 0.3mL 1-aza-12-crown 4-ether, 1.29g anhydrous lithium chloride, 2mL 3-aminopropyl triethoxysilane, 8mL tetraethyl orthosilicate and the Fe obtained in step one ₃ O ₄ /RGO was added to 20 mL of anhydrous ethanol, stirred evenly, then 30 mL of deionized water/ammonia mixture was added, and the reaction was carried out in a water bath at 25 °C for 8 h to obtain reaction product II;

The volume ratio of deionized water and ammonia water in the mixed solution of deionized water/ammonia water described in step 2 1. is 2:1, and the mass fraction of ammonia water is 30%;

②. First, use anhydrous ethanol to wash the reaction product II for 5 times, then use deionized water to wash the reaction product II for 3 to 5 times, and then use 35% hydrochloric acid to wash the reaction product II until ICP-AES can not detect Li ⁺ , then use deionized water to wash the reaction product II to pH 7, and finally vacuum dry at 50 °C to obtain Fe ₃ O ₄ @SiO ₂ @IIP/RGO, which is High anti-agglomeration RGO-based magnetic lithium-ion imprinted polymer.

Fig. 1 is the SEM image of the high anti-agglomeration RGO-based magnetic lithium ion imprinted polymer prepared in Example 1;

Fig. 2 is the SEM image of the high anti-agglomeration RGO-based magnetic lithium ion imprinted polymer prepared in Example 1;

FIG. 3 is a SEM image of the high-anti-agglomeration RGO-based magnetic lithium ion imprinted polymer prepared in Example 1. FIG.

By comparing Figures 1 to 3, it can be seen that most of the polymer nanoparticles prepared in Figure 3 are in the shape of a single sphere, with the best dispersibility; the polymer nanoparticles prepared in Figure 1 begin to agglomerate, but a single spherical shape can still be seen; The polymer nanoparticles prepared in Figure 2 have the most obvious agglomeration, and no single spherical shape can be seen. Therefore, when the mass ratio of RGO to Fe ₃ O ₄ is 3:1, the prepared RGO-based magnetic Li-ion imprinted polymer has the best anti-agglomeration properties.

Application performance measurement:

0.2 g of the high-anti-agglomeration RGO-based magnetic lithium ion imprinted polymer prepared in Examples 1 to 3 were respectively put into 250 mL of lithium ion-containing aqueous solution, the lithium ion concentration was 100 mg/L, the reaction was shaken, filtered, and the lithium ion concentration in the filtrate was measured. , and the results are shown in Table 1.

Table 1

As can be seen from Table 1, since the mass ratio (1:3) of RGO and Fe ₃ O ₄ added in Example 2 is the smallest, the agglomeration phenomenon is obvious, and the specific surface area is the smallest, so the adsorption amount of lithium ions is the smallest, which is 138.20 mg/g. In Example 3, the mass ratio of RGO to Fe ₃ O ₄ (3:1) is the largest, the anti-agglomeration effect is good, and the specific surface area is the largest, so the adsorption capacity is the best, and the adsorption capacity is 256.43 mg/g. In Example 1, the mass ratio of RGO and Fe ₃ O ₄ (1:1) was moderate, and its specific surface area and adsorption capacity were also in the middle, and the adsorption capacity was 151.22 mg/g; it is inferred from this that the addition amount of RGO within a certain range There is a positive correlation with the adsorption amount, and RGO has an obvious contribution to the anti-agglomeration effect of the polymer. The optimal mass ratio of RGO to Fe ₃ O ₄ in the preparation process is 3:1. It should be specially pointed out that the adsorption capacity of the existing magnetic lithium ion imprinted polymer is about 130-150 mg/g. The adsorption capacity of lithium ions was greatly improved by imprinted polymers.

The RGO-based magnetic lithium ion imprinted polymer with high anti-agglomeration properties proposed by the present invention and the preparation method thereof have been described by the examples, and those skilled in the art can obviously understand the content, spirit and scope of the present invention. The contents described above can be modified or appropriately modified and combined to realize the present invention. It should be particularly pointed out that all similar substitutions and modifications apparent to those skilled in the art are deemed to be included in the spirit, scope and content of the present invention.

Claims (10)

1. A preparation method of a high-agglomeration-resistance RGO-based magnetic lithium ion imprinted polymer is characterized by comprising the following steps:

firstly, dissolving reduced graphene oxide in deionized water, and then adding FeSO ₄ ·7H ₂ O and FeCl ₃ ·6H ₂ O, dropwise adding a NaOH solution under the conditions of water bath oscillation in a shaking table and nitrogen gas introduction into the solution, adjusting the pH value of the system, and finally carrying out water bath oscillation reaction in the shaking table under the protection of nitrogen gas atmosphere to obtain a reaction product I after the reaction is finished; cleaning and drying the reaction product to obtain Fe ₃ O ₄ /RGO；

II, preparing Fe ₃ O ₄ @SiO ₂ @IIP/RGO：

Firstly, 1-aza-12-crown 4-ether, anhydrous lithium chloride, 3-aminopropyl triethoxysilane, ethyl orthosilicate and Fe ₃ O ₄ adding/RGO into absolute ethyl alcohol, stirring uniformly, then adding a mixed solution of deionized water/ammonia water, and carrying out water bath oscillation reaction to obtain a reaction product II;

secondly, firstly, absolute ethyl alcohol is used for cleaning the reaction product II, then deionized water is used for cleaning the reaction product II, and hydrochloric acid is used for cleaning the reaction product II until ICP-AES can not detect Li ⁺ Then, the reaction product II is washed by deionized water and finally dried in vacuum to obtain Fe ₃ O ₄ @SiO ₂ And @ IIP/RGO is the high agglomeration resistant RGO-based magnetic lithium ion imprinted polymer.

2. The method for preparing the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer according to claim 1, wherein the mass-to-volume ratio of the reduced graphene oxide to the deionized water in the step one is (0.33 g-3 g): (60 mL-200 mL); FeSO described in step one ₄ ·7H ₂ The mass ratio of the O to the deionized water is (1.2 g-3.6 g) to (60 mL-200 mL); FeCl as described in step one ₃ ·6H ₂ The mass ratio of O to the volume ratio of deionized water is (2.33 g-6.99 g) to (60 mL-200 mL).

3. The method for preparing the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer according to claim 1, wherein the revolution number of the rotary table stirring in the first step is 60r/min to 120r/min, and the temperature of the water bath is 60 ℃ to 80 ℃; the reaction time in the first step is 1-2 h.

4. The preparation method of the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer as claimed in claim 1, wherein the pH value of the system in the first step is adjusted to 8-10; the drying temperature in the first step is 30-50 ℃; the concentration of the NaOH solution in the first step is 1 mol/L.

5. The preparation method of the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer as claimed in claim 1, wherein the temperature of the water bath in the second step is 25-30 ℃, and the reaction time is 6-8 h.

6. The method for preparing the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer as claimed in claim 1, wherein the volume ratio of the mixed solution of 1-aza-12-crown 4-ether, 3-aminopropyltriethoxysilane, tetraethoxysilane, absolute ethanol and deionized water/ammonia water in the second step is (0.3 mL-0.9 mL): (2 mL-6 mL): (8 mL-24 mL): (20 mL-60 mL): (30 mL-90 mL).

7. According to claim1, the preparation method of the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer is characterized in that anhydrous lithium chloride and Fe in the second step ₃ O ₄ The mass ratio of/RGO is (1.29-3.87 g) to (1.33-4 g).

8. The method for preparing the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer as claimed in claim 1, wherein the volume ratio of the mass of the anhydrous lithium chloride to the volume of the 1-aza-12-crown 4-ether in the second step (1.29-3.8 g) to the volume of the 1-aza-12-crown 4-ether in the second step (0.3-0.9 mL).

9. The preparation method of the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer as claimed in claim 1, wherein the volume ratio of deionized water to ammonia water in the deionized water/ammonia water mixed solution in the second step is 2:1, wherein the mass fraction of ammonia water is 25% -30%.

10. The preparation method of the high agglomeration resistance RGO-based magnetic lithium ion imprinted polymer as claimed in claim 1, wherein the temperature of vacuum drying in the second step is 50-60 ℃; secondly, firstly, the reaction product II is cleaned for 3 to 5 times by using absolute ethyl alcohol, then the reaction product II is cleaned for 3 to 5 times by using deionized water, and then the reaction product II is cleaned by using hydrochloric acid with the mass fraction of 35 to 40 percent until the ICP-AES can not detect Li ⁺ Then, the reaction product II is washed by deionized water until the pH value is 7, and finally dried in vacuum to obtain Fe ₃ O ₄ @SiO ₂ And @ IIP/RGO is the high agglomeration resistant RGO-based magnetic lithium ion imprinted polymer.

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