CN112591798A - Preparation method of columnar manganese lithium ion sieve compound - Google Patents

Preparation method of columnar manganese lithium ion sieve compound Download PDF

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CN112591798A
CN112591798A CN202011484088.0A CN202011484088A CN112591798A CN 112591798 A CN112591798 A CN 112591798A CN 202011484088 A CN202011484088 A CN 202011484088A CN 112591798 A CN112591798 A CN 112591798A
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lithium ion
ion sieve
manganese
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韩红静
马颖虎
张银龙
曾昭渭
郑永艳
赵鑫淼
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Qinghai University
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Abstract

The invention relates to the technical field of preparation of lithium ion sieve adsorbents, and particularly relates to a preparation method of a columnar manganese-based lithium ion sieve compound. Obtaining needle-shaped MnO by using hydrothermal reaction of potassium permanganate and ethanol2Powder, then MnO is added2Heat treating the powder in a muffle furnace to obtain Mn2O3Using Mn2O3Hydrothermal reaction with LiCl in alkaline environment to obtain LiMnO2Mixing LiMnO with2Obtaining Li with columnar morphology after heat treatment in a muffle furnace1.6Mn1.6O4A lithium ion sieve precursor by feedingAcid washing of step (a) to obtain H1.6Mn1.6O4The lithium ion sieve is synthesized to have a stable spinel structure. The method uses low cost MnO2And LiCl is used as a raw material, and the preparation method has the advantages of low cost, simple process, greenness, energy conservation and the like. The highest Li elution rate of the lithium ion sieve precursor can reach 94%, and the lowest Mn loss rate is 4.9%; the balance adsorption capacity of the prepared lithium ion sieve is 43mg/g at most, and after 6 times of acid washing and lithium extraction cycles, the solution loss of manganese can be maintained at 4.5% at least, so that the lithium ion sieve has a good application prospect.

Description

Preparation method of columnar manganese lithium ion sieve compound
Technical Field
The invention relates to the technical field of preparation of lithium ion sieve adsorbents, and particularly relates to a preparation method of a columnar manganese-based lithium ion sieve compound.
Background
Because of its excellent performance, metal lithium is widely used in various high and new technical fields such as lithium ion batteries, lithium isotope hydrogen bombs and the like, so that it plays an important role in economic development and national defense industry, and is an indispensable novel energy metal in the 21 st century. The total reserve of lithium resources, which has been ascertained worldwide, is about 3950 ten thousand tons, and is mainly distributed in the form of seawater, salt lake brine and stacked lithium ore. The traditional solid lithium ore lithium extraction technology can not meet the market demand far away due to the reasons of complicated steps, high mining cost, increasingly exhausted ore sources and the like, and the lithium resource storage amount in seawater and salt lake brine is very large and exceeds two thirds of the total lithium resource. Therefore, the development and utilization of liquid lithium resources attract the attention of many industries and fields, and become a new research hotspot.
The liquid state mine in China has abundant lithium resources, and particularly, the lithium resources in salt lake brine in Qinghai and Tibet are considerable. The lithium content of the brine of east-west tai gilel lake and Yilieng salt lake is 10 times of that of the American great salt lake, but the other remarkable characteristic of the salt lakes is that the ratio of magnesium to lithium is very high, and the magnesium-lithium ratio of some salt lake brine is dozens to hundreds of times higher than that of foreign countries. The high magnesium-lithium ratio is a major factor hindering the development of the industry for extracting lithium from brine in Qinghai province. The search for a reasonable lithium extraction method and the efficient extraction of lithium from the salt lake brine with high magnesium-lithium ratio are key tasks for promoting the development of the salt lake brine lithium extraction industry.
At present, the process for extracting lithium from salt lakes is endless, has different advantages and defects, and is suitable for extracting lithium from high magnesium-lithium ratio salt lake brine in China. Although the precipitation method is mature in technology, the precipitation method cannot be directly used for extracting lithium from salt lake brine with more alkaline earth metals and lower lithium content; the solvent extraction method has good selectivity, but has high cost and certain pollution and damage to the ecological environment; the calcination leaching method has not ideal economic benefit; the carbonization method has a small application range and is only suitable for carbonate salt lakes. The method comprehensively considers the advantages and the disadvantages of various methods for extracting the lithium resource from the salt lake brine, and compared with other methods, the adsorption method is more suitable for extracting lithium from the salt lake brine with high magnesium-lithium ratio in China, wherein the ion sieve adsorbent has low cost, is green and environment-friendly, has high selective adsorption and shows better application prospect. Therefore, research and development of efficient and green ion sieve adsorbents have great significance for separating and extracting lithium from brine with high magnesium-lithium ratio by an adsorption method, which is also the key for developing lithium resources in salt lakes in China, and research on optimizing the preparation method, improving the structural stability, improving the lithium ion adsorption performance and the like of the lithium adsorbents is the important factor for the development of the lithium industry in China.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of a columnar manganese-based lithium ion sieve compound.
The invention relates to a preparation method of a columnar manganese lithium ion sieve compound, which comprises the following steps:
step one, dissolving potassium permanganate in water, continuously dropwise adding anhydrous ethanol with the volume of 2.5mL, stirring for 0.5-1 h, and placing in a 50mL hydrothermal reaction kettle for reaction, wherein the reaction temperature is 100-150 ℃, and the reaction time is 15-20 h; after the reaction, obtaining brown precipitate by vacuum filtration, deionized water flushing and drying, and carrying out heat treatment on the dried brown precipitate in a muffle furnace to obtain needle-shaped MnO2Wherein the heat treatment temperature is 300-400 ℃, and the heat preservation time is 1-2 h to obtain needle MnO2；
Step two, adding acicular MnO2Heat treatment in a muffle furnace to obtain acicular Mn2O3Powder, wherein the treatment temperature is 700-900 ℃, and the treatment time is 5-15 h;
step three, taking Mn2O3Uniformly mixing the mixture and LiCl to obtain a mixture, dissolving the mixture in 50mL of water, adding KOH to adjust the pH value of the solution to be 13-15, placing the uniformly stirred solution into a 50mL hydrothermal reaction kettle, placing the kettle into an oven for heat treatment at the temperature of 150-180 ℃, keeping the temperature for 8-15 h, and finally obtaining needle-shaped LiMnO by vacuum filtration, deionized water washing and drying2Powder;
step four, adding acicular LiMnO2The powder is thermally treated in a muffle furnace to obtain a columnar manganese-based lithium ion sieve precursor Li1.6Mn1.6O4Wherein the heat treatment temperature is 400-500 ℃, and the heat preservation time is 3-6 h;
step five, taking a certain amount of the lithium ion sieve precursor Li prepared by the method1.6Mn1.6O4Placing the mixture into a hydrochloric acid solution with the concentration of 0.1-0.15 mol/L, stirring at the constant temperature of 25 ℃, reacting for 20-24 h, and removing Li in the precursor+Then obtaining the columnar manganese lithium ion sieve H by vacuum filtration, deionized water washing and 120 ℃ drying1.6Mn1.6O4。
The optimized preparation method of the columnar manganese lithium ion sieve compound specifically comprises the following steps:
step one, dissolving potassium permanganate in water, continuously dropwise adding anhydrous ethanol with the volume of 2.5mL, stirring for 0.5h, and placing the mixture in a 50mL hydrothermal reaction kettle for reaction, wherein the reaction temperature is 150 ℃, and the reaction time is 20 h; after the reaction, obtaining brown precipitate by vacuum filtration, deionized water flushing and drying, and carrying out heat treatment on the dried brown precipitate in a muffle furnace to obtain needle-shaped MnO2Wherein the heat treatment temperature is 350 ℃, the heat preservation time is 1.5h, and the needle-shaped MnO is obtained2。
Step two, adding acicular MnO2Heat treatment in a muffle furnace to obtain acicular Mn2O3Powder, wherein the treatment temperature is 800 ℃ and the treatment time is 15 h.
Step three, taking Mn2O3And LiCl to obtain a mixture,dissolving the mixture in 50mL of water at a molar ratio of lithium element to manganese element of 2:1, adding KOH to adjust the pH value of the solution to 15, placing the uniformly stirred solution in a 50mL hydrothermal reaction kettle, placing the kettle in an oven for heat treatment at 180 ℃, keeping the temperature for 8 hours, and finally obtaining needle-shaped LiMnO by vacuum filtration, deionized water washing and drying2And (3) powder.
Step four, adding acicular LiMnO2The powder is thermally treated in a muffle furnace to obtain a columnar manganese-based lithium ion sieve precursor Li1.6Mn1.6O4Wherein the heat treatment temperature is 450 ℃, and the heat preservation time is 4 h;
step five, taking a certain amount of the lithium ion sieve precursor Li prepared by the method1.6Mn1.6O4Placing the solution in hydrochloric acid solution with the concentration of 0.15mol/L, stirring at the constant temperature of 25 ℃, reacting for 24 hours, and removing Li in the precursor+Then obtaining the columnar manganese lithium ion sieve H by vacuum filtration, deionized water washing and 120 ℃ drying1.6Mn1.6O4。
Further, in the first step, the water dissolved by the potassium permanganate is deionized water.
Further, the columnar manganese lithium ion sieve H prepared by the method1.6Mn1.6O4Can be used for extracting lithium from salt lake brine with high magnesium-lithium ratio.
Compared with the prior art, the invention has the following beneficial effects: the manganese-based lithium ion sieve with the columnar morphology is prepared by a hydrothermal method, and the synthesized lithium ion sieve has a stable spinel structure. The method uses low cost MnO2And LiCl is used as a raw material, and the preparation method has the advantages of low cost, simple process, greenness, energy conservation and the like. The highest Li elution rate of the lithium ion sieve precursor can reach 94%, and the lowest Mn loss rate is 4.9%; the balance adsorption capacity of the prepared lithium ion sieve is 43mg/g at most, and after 6 times of acid washing and lithium extraction cycles, the solution loss of manganese can be maintained at 4.5% at least, so that the lithium ion sieve has a good application prospect.
Drawings
FIG. 1 shows a manganese-based lithium ion sieve precursor Li according to the present invention1.6Mn1.6O4Low power (2000X) SEM images of;
FIG. 2 shows a manganese-based lithium ion sieve precursor Li according to the present invention1.6Mn1.6O4High power (10000X) SEM images of;
FIG. 3 shows a precursor Li of the columnar manganese-based lithium ion sieve of the present invention1.6Mn1.6O4XRD pattern of (a);
FIG. 4 shows a precursor Li of the cylindrical manganese-based lithium ion sieve in example 1 of the present invention1.6Mn1.6O4A time-dependent change curve of the elution rate of lithium and the dissolution loss rate of manganese during acid washing;
FIG. 5 shows a cylindrical manganese-based lithium ion sieve H in example 1 of the present invention1.6Mn1.6O4The relationship between the cycle number of lithium extraction and the manganese dissolution rate is shown.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The invention relates to a preparation method of a columnar manganese lithium ion sieve compound, which comprises the following steps:
step one, weighing 1.5g of potassium permanganate, dissolving in 32.5mL of deionized water, continuously dropwise adding 2.5mL of absolute ethyl alcohol, stirring for 0.5h, and placing in a 50mL hydrothermal reaction kettle for reaction, wherein the reaction temperature is 150 ℃ and the reaction time is 20 h; after the reaction, obtaining brown precipitate by vacuum filtration, deionized water flushing and drying, and carrying out heat treatment on the dried brown precipitate in a muffle furnace to obtain needle-shaped MnO2Wherein the heat treatment temperature is 350 ℃, the heat preservation time is 1.5h, and the needle-shaped MnO is obtained2；
Step two, adding acicular MnO2Heat treatment in a muffle furnace to obtain acicular Mn2O3Powder, wherein the treatment temperature is 800 ℃, and the treatment time is 15 hours;
step three, taking Mn2O3Uniformly mixing the LiMnO powder and LiCl to obtain a mixture, dissolving the mixture in 50mL of water, adding KOH to adjust the pH value of the solution to be 15, placing the uniformly stirred solution into a 50mL hydrothermal reaction kettle, placing the kettle in an oven to perform heat treatment at 180 ℃, keeping the temperature for 8 hours, and finally obtaining needle-shaped LiMnO through vacuum filtration, deionized water washing and drying2Powder;
step four, adding acicular LiMnO2The powder is thermally treated in a muffle furnace to obtain a columnar manganese-based lithium ion sieve precursor Li1.6Mn1.6O4Wherein the heat treatment temperature is 450 ℃, and the heat preservation time is 4 h. Lithium ion sieve precursor Li1.6Mn1.6O4The obtained lithium ion sieve has uniform particle size and is shown in a columnar shape from a lithium ion sieve precursor Li1.6Mn1.6O4The XRD pattern (see the attached figure 3 for details) shows that the prepared lithium ion sieve precursor Li1.6Mn1.6O4The purity is high, and the structure is a spinel structure;
step five, accurately weighing 0.5g of lithium ion sieve precursor Li prepared by the method1.6Mn1.6O4Placing the mixture into 500mL hydrochloric acid solution with the concentration of 0.15mol/L, stirring at the constant temperature of 25 ℃, reacting for 24 hours, and removing Li in the precursor+The elution rate of Li and the dissolution loss rate of Mn in the process are respectively 92% and 5%, which are detailed in the precursor Li of the columnar manganese-based lithium ion sieve1.6Mn1.6O4The change curve of the elution rate of lithium and the manganese dissolution loss rate with time (shown in figure 4) in acid washing is carried out, and then the columnar manganese-based lithium ion sieve H is obtained after vacuum filtration, deionized water washing and 120 ℃ drying1.6Mn1.6O4。
0.5g of lithium ion sieve was weighed into 500mL of Li+In the solution with the concentration of 150mg/L, the pH value of the solution is 10, the adsorption balance is achieved after 24 hours, the measured equilibrium adsorption capacity is 42mg/g, and after 6 acid washing and lithium extraction cycles, the dissolution loss of manganese can be maintained at 4.5 percent, which is detailed in a columnar manganese systemLithium ion sieve H1.6Mn1.6O4FIG. 5 shows the relationship between the number of cycles of lithium extraction and the manganese dissolution rate, and it can be seen that the column shape H is1.6Mn1.6O4The lithium ion sieve has better stability.
Example 2
The invention relates to a preparation method of a columnar manganese lithium ion sieve compound, which comprises the following steps:
step one, weighing 1.5g of potassium permanganate, dissolving in 32.5mL of deionized water, continuously dropwise adding 2.5mL of absolute ethyl alcohol, stirring for 0.5h, and placing in a 50mL hydrothermal reaction kettle for reaction, wherein the reaction temperature is 150 ℃ and the reaction time is 20 h; after the reaction, obtaining brown precipitate by vacuum filtration, deionized water flushing and drying, and carrying out heat treatment on the dried brown precipitate in a muffle furnace to obtain needle-shaped MnO2Wherein the heat treatment temperature is 350 ℃, the heat preservation time is 1.5h, and the needle-shaped MnO is obtained2；
Step two, adding acicular MnO2Heat treatment in a muffle furnace to obtain acicular Mn2O3Powder, wherein the treatment temperature is 800 ℃, and the treatment time is 15 hours;
step three, taking Mn2O3Uniformly mixing the LiMnO powder and LiCl to obtain a mixture, dissolving the mixture in 50mL of water, adding KOH to adjust the pH value of the solution to be 14, placing the uniformly stirred solution into a 50mL hydrothermal reaction kettle, placing the kettle in an oven for heat treatment at the temperature of 150 ℃, keeping the temperature for 8 hours, and finally obtaining needle-shaped LiMnO through vacuum filtration, deionized water washing and drying2Powder;
step four, adding acicular LiMnO2The powder is thermally treated in a muffle furnace to obtain a columnar manganese-based lithium ion sieve precursor Li1.6Mn1.6O4Wherein the heat treatment temperature is 450 ℃, and the heat preservation time is 5 h;
step five, accurately weighing 0.5g of lithium ion sieve precursor Li prepared by the method1.6Mn1.6O4Placing in 500mL hydrochloric acid solution with concentration of 0.15mol/L, stirring at constant temperature of 25 ℃, reacting for 24h, and removing precursorLi in bulk+In the process, the Li elution rate and the Mn dissolution loss rate are respectively 89% and 6.2%, and then the columnar manganese-based lithium ion sieve H is obtained by vacuum filtration, deionized water washing and 120 ℃ drying1.6Mn1.6O4。
0.5g of lithium ion sieve was weighed into 500mL of Li+In the solution with the concentration of 150mg/L, the pH value of the solution is 10, the adsorption balance is achieved after 24 hours, the measured equilibrium adsorption capacity is 40mg/g, and the dissolution loss of manganese can be maintained at 5% after 6 acid washing and lithium extraction cycles.
Example 3
The invention relates to a preparation method of a columnar manganese lithium ion sieve compound, which comprises the following steps:
step one, weighing 1.5g of potassium permanganate, dissolving in deionized water, continuously dropwise adding 2.5mL of absolute ethyl alcohol, stirring for 0.5h, and placing in a 50mL hydrothermal reaction kettle for reaction, wherein the reaction temperature is 150 ℃, and the reaction time is 20 h; after the reaction, obtaining brown precipitate by vacuum filtration, deionized water flushing and drying, and carrying out heat treatment on the dried brown precipitate in a muffle furnace to obtain needle-shaped MnO2Wherein the heat treatment temperature is 350 ℃, the heat preservation time is 1.5h, and the needle-shaped MnO is obtained2；
Step two, adding acicular MnO2Heat treatment in a muffle furnace to obtain acicular Mn2O3Powder, wherein the treatment temperature is 800 ℃, and the treatment time is 15 hours;
step three, taking Mn2O3Uniformly mixing the LiMnO solution and LiCl to obtain a mixture, dissolving the mixture in 50mL of water, adding KOH to adjust the pH value of the solution to be 15, placing the uniformly stirred solution into a 50mL hydrothermal reaction kettle, placing the kettle in an oven to perform heat treatment at 180 ℃, keeping the temperature for 15 hours, and finally obtaining needle-shaped LiMnO through vacuum filtration, deionized water washing and drying2Powder;
step four, adding acicular LiMnO2The powder is thermally treated in a muffle furnace to obtain a columnar manganese-based lithium ion sieve precursor Li1.6Mn1.6O4Wherein the heat treatment temperature is 450 deg.CKeeping the temperature at 6 h;
step five, accurately weighing 0.5g of lithium ion sieve precursor Li prepared by the method1.6Mn1.6O4Placing the mixture into 500mL hydrochloric acid solution with the concentration of 0.15mol/L, stirring at the constant temperature of 25 ℃, reacting for 24 hours, and removing Li in the precursor+In the process, the Li elution rate and the Mn dissolution loss rate are respectively 93 percent and 4.9 percent, and then the columnar manganese-based lithium ion sieve H is obtained by vacuum filtration, deionized water washing and 120 ℃ drying1.6Mn1.6O4。
0.5g of lithium ion sieve was weighed into 500mL of Li+In the solution with the concentration of 150mg/L, the pH value of the solution is 10, the adsorption balance is achieved after 24 hours, the measured equilibrium adsorption capacity is 43mg/g, and the dissolution loss of manganese can be maintained at 5% after 6 acid washing and lithium extraction cycles.
Example 4
The invention relates to a preparation method of a columnar manganese lithium ion sieve compound, which comprises the following steps:
step one, weighing 1.5g of potassium permanganate, dissolving in deionized water, continuously dropwise adding 2.5mL of absolute ethyl alcohol, stirring for 1h, and placing in a 50mL hydrothermal reaction kettle for reaction, wherein the reaction temperature is 100 ℃, and the reaction time is 15 h; after the reaction, obtaining brown precipitate by vacuum filtration, deionized water flushing and drying, and carrying out heat treatment on the dried brown precipitate in a muffle furnace to obtain needle-shaped MnO2Wherein the heat treatment temperature is 300 ℃, the heat preservation time is 2 hours, and the needle-shaped MnO is obtained2；
Step two, adding acicular MnO2Heat treatment in a muffle furnace to obtain acicular Mn2O3Powder, wherein the treatment temperature is 700 ℃ and the treatment time is 5 h;
step three, taking Mn2O3Uniformly mixing the manganese element and LiCl to obtain a mixture, dissolving the mixture in 50mL of water, adding KOH to adjust the pH value of the solution to be 13, placing the uniformly stirred solution into a 50mL hydrothermal reaction kettle, placing the kettle in an oven for heat treatment at 150 ℃, keeping the temperature for 8 hours, and finally obtaining the lithium manganeseObtaining needle-like LiMnO2Powder;
step four, adding acicular LiMnO2The powder is thermally treated in a muffle furnace to obtain a columnar manganese-based lithium ion sieve precursor Li1.6Mn1.6O4Wherein the heat treatment temperature is 400 ℃, and the heat preservation time is 3 h.
Step five, accurately weighing 0.5g of lithium ion sieve precursor Li prepared by the method1.6Mn1.6O4Placing the mixture into 500mL hydrochloric acid solution with the concentration of 0.1mol/L, stirring at the constant temperature of 25 ℃, reacting for 20h, and removing Li in the precursor+In the process, the Li elution rate and the Mn dissolution loss rate are respectively 89.5 percent and 5.1 percent, and then the columnar manganese lithium ion sieve H is obtained by vacuum filtration, deionized water washing and 120 ℃ drying1.6Mn1.6O4。
0.5g of lithium ion sieve was weighed into 500mL of Li+In the solution with the concentration of 150mg/L, the pH value of the solution is 10, the adsorption balance is achieved after 24 hours, the measured equilibrium adsorption capacity is 40.5mg/g, and the dissolution loss of manganese can be maintained at 4.8% after 6 acid washing and lithium extraction cycles.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (4)

1. The preparation method of the columnar manganese lithium ion sieve compound is characterized by comprising the following steps:
step one, dissolving potassium permanganate in water, continuously dropwise adding anhydrous ethanol with the volume of 2.5mL, stirring for 0.5-1 h, and placing in a 50mL hydrothermal reaction kettle for reaction, wherein the reaction temperature is 100-150 ℃, and the reaction time is 15-20 h; after the reaction, obtaining brown precipitate by vacuum filtration, deionized water flushing and drying, and carrying out heat treatment on the dried brown precipitate in a muffle furnace to obtain needle-shaped MnO2Wherein the heat treatment temperature is 300-400 ℃, the heat preservation time is 1-2 h, and the needle is obtainedForm MnO of2；
Step two, adding acicular MnO2Heat treatment in a muffle furnace to obtain acicular Mn2O3Powder, wherein the treatment temperature is 700-900 ℃, and the treatment time is 5-15 h;
step three, taking Mn2O3Uniformly mixing the mixture and LiCl to obtain a mixture, dissolving the mixture in 50mL of water, adding KOH to adjust the pH value of the solution to be 13-15, placing the uniformly stirred solution into a 50mL hydrothermal reaction kettle, placing the kettle into an oven for heat treatment at the temperature of 150-180 ℃, keeping the temperature for 8-15 h, and finally obtaining needle-shaped LiMnO by vacuum filtration, deionized water washing and drying2Powder;
step four, adding acicular LiMnO2The powder is thermally treated in a muffle furnace to obtain a columnar manganese-based lithium ion sieve precursor Li1.6Mn1.6O4Wherein the heat treatment temperature is 400-500 ℃, and the heat preservation time is 3-6 h;
step five, taking a certain amount of the lithium ion sieve precursor Li prepared by the method1.6Mn1.6O4Placing the mixture into a hydrochloric acid solution with the concentration of 0.1-0.15 mol/L, stirring at the constant temperature of 25 ℃, reacting for 20-24 h, and removing Li in the precursor+Then obtaining the columnar manganese lithium ion sieve H by vacuum filtration, deionized water washing and 120 ℃ drying1.6Mn1.6O4。
2. The method for preparing a columnar manganese-based lithium ionic sieve compound according to claim 1, which is characterized by comprising the following steps:
step one, dissolving potassium permanganate in water, continuously dropwise adding anhydrous ethanol with the volume of 2.5mL, stirring for 0.5h, and placing the mixture in a 50mL hydrothermal reaction kettle for reaction, wherein the reaction temperature is 150 ℃, and the reaction time is 20 h; after the reaction, obtaining brown precipitate by vacuum filtration, deionized water flushing and drying, and carrying out heat treatment on the dried brown precipitate in a muffle furnace to obtain needle-shaped MnO2Wherein the heat treatment temperature is 350 ℃, and the heat preservation time is 1.5h, and needle-shaped is obtainedMnO2。
Step two, adding acicular MnO2Heat treatment in a muffle furnace to obtain acicular Mn2O3Powder, wherein the treatment temperature is 800 ℃ and the treatment time is 15 h.
Step three, taking Mn2O3Uniformly mixing the mixture and LiCl to obtain a mixture, dissolving the mixture in 50mL of water, adding KOH to adjust the pH value of the solution to be 15, placing the uniformly stirred solution into a 50mL hydrothermal reaction kettle, placing the kettle in an oven to carry out heat treatment at 180 ℃, keeping the temperature for 8 hours, and finally obtaining needle-shaped LiMnO through vacuum filtration, deionized water washing and drying2And (3) powder.
Step four, adding acicular LiMnO2The powder is thermally treated in a muffle furnace to obtain a columnar manganese-based lithium ion sieve precursor Li1.6Mn1.6O4Wherein the heat treatment temperature is 450 ℃, and the heat preservation time is 4 h;
step five, taking a certain amount of the lithium ion sieve precursor Li prepared by the method1.6Mn1.6O4Placing the solution in hydrochloric acid solution with the concentration of 0.15mol/L, stirring at the constant temperature of 25 ℃, reacting for 24 hours, and removing Li in the precursor+Then obtaining the columnar manganese lithium ion sieve H by vacuum filtration, deionized water washing and 120 ℃ drying1.6Mn1.6O4。
3. The method of claim 1 or 3, wherein in the first step, the water dissolved by potassium permanganate is deionized water.
4. The method of claim 1 or 2, wherein the manganese-based lithium ion sieve precursor Li is prepared by the method1.6Mn1.6O4Can be used for extracting lithium from salt lake brine with high magnesium-lithium ratio.
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