A manganese-based lithium ion sieve based on electrolytic manganese anode mud and its preparation method

Abstract

The invention discloses a manganese-based lithium ion sieve based on electrolytic manganese anode mud and a preparation method thereof. The preparation method comprises the following steps: S1: obtaining electrolytic manganese anode mud, calcining and reducing it at high temperature, and grinding it to obtain a mixture powder of Mn2O3; S2: mixing acetic acid or an acetate solution with the mixture powder, stirring and leaching it at a constant temperature, filtering, and drying to obtain a mixture powder of Mn2O3; S3: using LiOH·H2O as a lithium source, the mixture powder as a manganese source, and ethanol as a solvent, mixing them evenly, sealing them, and performing a heat-insulating reaction, filtering, washing, and drying the reaction product to obtain E-LiMnO2; S4: calcining the E-LiMnO2 at high temperature to obtain a precursor product E-Li 1.6 Mn 1.6 O4; S5: for the precursor product E-Li 1.6 Mn 1.6 O4 was acid leached, and the acid leached product was filtered, washed and dried to obtain manganese-based lithium ion sieve E-H 1.6 Mn 1.6 The present invention can use solid waste electrolytic manganese anode mud to prepare a manganese-based lithium ion sieve with larger adsorption capacity, better ion selectivity and better recycling regeneration stability.

Description

Technical Field

[0001] The present invention relates to the technical field of manganese-based lithium ion sieves, and in particular to a manganese-based lithium ion sieve based on electrolytic manganese anode mud and a preparation method thereof. Background Art

[0002] Lithium has a wide range of uses and abundant resources. Brine-based lithium resources account for approximately 65-66% of total lithium reserves. However, the rapidly growing demand for lithium resources is leading to a severe shortage. Therefore, the exploration and utilization of unconventional lithium resources, including geothermal brines, seawater, and gas field produced water, has become imperative. Methods for extracting lithium from liquid lithium resources include traditional evaporation and precipitation, solvent extraction, adsorption, electrochemical methods, membrane separation, and reaction-coupled separation. Among these, adsorption has attracted significant attention due to its high lithium selectivity, simple and efficient operation, high cost-effectiveness, and minimal environmental impact.

[0003] Commonly used adsorbents for adsorption methods include aluminum-based, titanium-based, and manganese-based adsorbents. The theoretical adsorption capacity of aluminum-based adsorbents is significantly lower than that of titanium- and manganese-based adsorbents. While titanium-based adsorbents have higher adsorption capacities, they also have significant disadvantages, including high cost and long adsorption times. Consequently, manganese-based adsorbents are receiving increasing attention in this field.

[0004] In manganese-based adsorbents, Li 1.6 Mn 1.6 O4 manganese-based lithium ion sieve adsorbents offer the highest adsorption capacity and excellent resistance to dissolution loss. Current preparation methods typically use chemical raw materials as synthetic raw materials, but these methods suffer from high energy consumption, long reaction times, uneven raw material contact, and incomplete reactions. To achieve even better adsorption performance, the adsorbents are modified by doping or coating. Existing modification methods essentially involve adding a modification step to the synthesis process, resulting in high energy consumption, long synthesis cycles, and high costs. Summary of the Invention

[0005] In view of the above problems, the present invention aims to provide a manganese-based lithium ion sieve based on electrolytic manganese anode mud and a preparation method thereof.

[0006] The technical solutions of the present invention are as follows:

[0007] In one aspect, a method for preparing a manganese-based lithium ion sieve based on electrolytic manganese anode mud is provided, comprising the following steps:

[0008] S1: Obtain electrolytic manganese anode mud, perform high-temperature roasting and reduction on the electrolytic manganese anode mud, and grind it to obtain a Mn2O3 mixture powder 1;

[0009] S2: mixing acetic acid or acetate solution with the Mn2O3 mixture powder 1, stirring and leaching at a constant temperature, filtering and drying to obtain the Mn2O3 mixture powder 2;

[0010] S3: Using LiOH·H2O as a lithium source, the Mn2O3 mixture powder as a manganese source, and ethanol as a solvent, the mixture is evenly mixed, sealed, and subjected to heat preservation reaction. The reaction product is filtered, washed, and dried to obtain E-LiMnO2;

[0011] S4: calcining the E-LiMnO2 at high temperature to obtain the precursor product E-Li 1.6 Mn 1.6 O4;

[0012] S5: the precursor product E-Li 1.6 Mn 1.6 O4 is acid leached, and then the acid leached product is filtered, washed and dried to obtain manganese-based lithium ion sieve EH 1.6 Mn 1.6 O4.

[0013] Preferably, in step S1, the high-temperature calcination reduction is performed at a temperature of 750-900° C. and a time of 10-90 minutes.

[0014] Preferably, in step S2, the concentration of the acetic acid or acetate solution is 1.5-4 mol / L, and the liquid-to-solid ratio during mixing is 8-12 mL:1 g; the temperature of the constant temperature stirring leaching is 70-90° C., the time is 10-60 min, and the stirring rate is 250-500 rpm.

[0015] Preferably, in step S3, the mass ratio of the lithium source to the manganese source is 2-8:1, and the volume fraction of the ethanol is 20-80%.

[0016] Preferably, in step S3, the temperature for the insulation reaction is 140-180° C., and the time is 12-24 hours.

[0017] Preferably, in step S4, the high-temperature calcination is performed at a temperature of 410-450° C. and for a time of 4-8 hours.

[0018] Preferably, in step S4, when performing high-temperature calcination, the temperature is increased to the target high-temperature calcination temperature at a heating rate of 6°C / min.

[0019] Preferably, in step S5, hydrochloric acid is used for acid leaching.

[0020] Preferably, the concentration of the hydrochloric acid is 0.2-0.6 mol / L, and the hydrochloric acid reacts with the precursor product E-Li 1.6 Mn1.6 The ratio of O4 is 200-500mL:1g, and the acid leaching time is 12-36h.

[0021] On the other hand, a manganese-based lithium ion sieve based on electrolytic manganese anode mud is also provided, which is prepared by using any of the above-mentioned methods for preparing a manganese-based lithium ion sieve based on electrolytic manganese anode mud.

[0022] The beneficial effects of the present invention are:

[0023] This method uses electrolytic manganese anode mud as raw material, removes heavy metal impurities through roasting and leaching pretreatment to obtain high-purity Mn2O3 doped with modified metal elements such as Fe, Al, and Pb. Then, using LiOH·H2O as a lithium source and ethanol as a solvent, a heat preservation reaction, high-temperature calcination, and acid leaching are performed to produce a manganese-based lithium ion sieve with high adsorption capacity, good ion selectivity, and excellent cyclic regeneration stability. This method not only facilitates the recycling of hazardous solid waste but also contributes to the development of lithium resource recovery technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0025] Figure 1 Schematic diagram of the process products of Example 2 and Comparative Example 1; wherein, Figure 1 (a) and Figure 1 (c) Transmission electron microscopy (TEM) images of LMO and E-LMO, respectively; Figure 1 (b) and Figure 1 (d) Selected area electron diffraction (SAED) images of LMO and E-LMO, respectively. DETAILED DESCRIPTION

[0026] The present invention is further described below with reference to the accompanying drawings and examples. It should be noted that, in the absence of conflict, the embodiments in this application and the technical features in the embodiments can be combined with each other. It should be noted that, unless otherwise specified, all technical and scientific terms used in this application have the same meanings as those commonly understood by those of ordinary skill in the art to which this application belongs. The use of similar words such as "include" or "comprising" in the present invention means that the elements or objects appearing before the word cover the elements or objects listed after the word and their equivalents, without excluding other elements or objects.

[0027] In one aspect, the present invention provides a method for preparing a manganese-based lithium ion sieve based on electrolytic manganese anode mud, comprising the following steps:

[0028] S1: Obtain electrolytic manganese anode mud, perform high-temperature roasting and reduction on the electrolytic manganese anode mud, and grind it to obtain a Mn2O3 mixture powder 1.

[0029] In a specific embodiment, the high temperature calcination reduction is performed at a temperature of 750-900° C. for 10-90 minutes. Optionally, during the high temperature calcination reduction, the temperature is increased to the target high temperature calcination reduction temperature at a heating rate of 5° C. / min.

[0030] S2: Mixing acetic acid or acetate solution with the Mn2O3 mixture powder 1, stirring and leaching at a constant temperature, filtering and drying to obtain the Mn2O3 mixture powder 2.

[0031] In a specific embodiment, the concentration of the acetic acid or acetate solution is 1.5-4 mol / L, the liquid-to-solid ratio during mixing is 8-12 mL:1 g, the constant temperature stirring leaching temperature is 70-90°C, the time is 10-60 minutes, and the stirring rate is 250-500 rpm. Optionally, the acetate is ammonium acetate or sodium acetate.

[0032] S3: Using LiOH·H2O as a lithium source, the Mn2O3 mixture powder as a manganese source, and ethanol as a solvent, the mixture is evenly mixed, sealed, and subjected to heat preservation reaction. The reaction product is filtered, washed, and dried to obtain E-LiMnO2.

[0033] In a specific embodiment, the mass ratio of the lithium source to the manganese source is 2-8:1, the volume fraction of the ethanol is 20-80%, and the temperature for the insulation reaction is 140-180° C. for 12-24 hours.

[0034] In the above embodiment, the present invention uses ethanol as a solvent, which can reduce the reaction temperature and achieve more uniform mixing of raw materials compared to aqueous solutions at the same temperature, thereby achieving a higher product purity.

[0035] S4: calcining the E-LiMnO2 at high temperature to obtain the precursor product E-Li 1.6 Mn 1.6 O4.

[0036] In a specific embodiment, the high temperature calcination is performed at a temperature of 410-450° C. for 4-8 hours. Optionally, during the high temperature calcination, the temperature is increased to the target high temperature calcination temperature at a heating rate of 6° C. / min.

[0037] S5: the precursor product E-Li 1.6Mn 1.6 O4 is acid leached, and then the acid leached product is filtered, washed and dried to obtain manganese-based lithium ion sieve EH 1.6 Mn 1.6 O4.

[0038] In a specific embodiment, hydrochloric acid is used for acid leaching, and the concentration of the hydrochloric acid is 0.2-0.6 mol / L. The hydrochloric acid reacts with the precursor product E-Li 1.6 Mn 1.6 The ratio of O4 is 200-500mL:1g, and the acid leaching time is 12-36h.

[0039] It should be noted that acid leaching is mainly used to activate the precursor product to obtain the ion sieve. In addition to the hydrochloric acid preferred in this embodiment, acid solutions such as sulfuric acid and nitric acid in the prior art can also be applied to the present invention.

[0040] The present invention uses electrolytic manganese anode mud as raw material. This solid waste is generated during the electrolysis of the manganese anode chamber and contains over 40% heavy metal components, including Mn, Pb, Se, and trace elements such as Pb, Fe, and Al. During the preparation process of the present invention, these heavy metals can be conditionally doped into the manganese-based lithium ion sieve, changing the crystal's dominant surface area and increasing the adsorption specific surface area, thereby enhancing the manganese-based lithium ion sieve's lithium adsorption performance. The manganese-based lithium ion sieve prepared by the preparation method of the present invention has a large adsorption capacity, good ion selectivity, and excellent recycling stability, and helps reduce the risk of solid waste pollution to the environment.

[0041] On the other hand, the present invention also provides a manganese-based lithium ion sieve based on electrolytic manganese anode mud, which is prepared by using any of the above-mentioned methods for preparing a manganese-based lithium ion sieve based on electrolytic manganese anode mud.

[0042] Example 1

[0043] A manganese-based lithium ion sieve based on electrolytic manganese anode mud is prepared by the following steps:

[0044] (1) obtaining electrolytic manganese anode mud, placing the electrolytic manganese anode mud into a muffle furnace, heating the temperature to 900° C. at a heating rate of 5° C. / min, calcining and reducing the electrolytic manganese anode mud at 900° C. for 30 min, and grinding the mixture powder of Mn2O3 to obtain a mixture powder;

[0045] In this embodiment, the electrolytic manganese anode mud is provided by a company in Guangxi. The main chemical components and contents of the electrolytic manganese anode mud are shown in Table 1:

[0046] Table 1 Main chemical composition and content of electrolytic manganese anode mud (wt%)

[0047] Element Mn Pb S Fe Al As Cu Content 68.6036 7.2893 0.6025 0.1983 0.1974 0.076 0.0154

[0048] (2) 2 mol / L ammonium acetate solution and the Mn2O3 mixture powder 1 were mixed at a solid-liquid ratio of 10:1, and stirred in a water bath at 80°C for 10 min. The stirring speed was maintained at 300 rpm during the process. After filtering and drying, the Mn2O3 mixture powder 2 was obtained.

[0049] (3) Using LiOH·H2O as the lithium source (8 g), the Mn2O3 mixture powder as the manganese source (4 g), and ethanol as the solvent (the volume fraction of ethanol is 28.57%), the mixture was evenly mixed and then transferred to a sealed hydrothermal reactor;

[0050] (4) placing the hydrothermal reactor in an oven at 160° C. for 24 h, filtering, washing, and drying the reaction product to obtain E-LiMnO 2 ;

[0051] (5) The E-LiMnO2 was placed in a muffle furnace, heated to 410°C at a heating rate of 6°C / min, and calcined at 410°C for 4 hours to obtain the precursor product E-Li 1.6 Mn 1.6 O4 (denoted as E-LMO);

[0052] (6) the precursor product E-Li 1.6 Mn 1.6 O4 is acid-leached with hydrochloric acid at a concentration of 0.5 mol / L. The hydrochloric acid reacts with the precursor product E-Li 1.6 Mn 1.6 The ratio of O4 is 200mL:1g, the acid leaching time is 24h, and then the acid leaching product is filtered, washed and dried to obtain manganese-based lithium ion sieve EH 1.6 Mn 1.6 O4 (denoted as E-HMO).

[0053] Example 2

[0054] Different from Example 1, the ratio of lithium source to manganese source in step (3) of this example is 4:1, that is, the amount of LiOH·H2O used is 8 g, and the amount of the second Mn2O3 mixture powder used is 2 g.

[0055] Example 3

[0056] Different from Example 1, the ratio of lithium source to manganese source in step (3) of this example is 6:1, that is, the amount of LiOH·H2O used is 8 g, and the amount of the second Mn2O3 mixture powder used is 1.33 g.

[0057] Example 4

[0058] Different from Example 1, the ratio of lithium source to manganese source in step (3) of this example is 8:1, that is, the amount of LiOH·H2O used is 8 g, and the amount of the second Mn2O3 mixture powder used is 1 g.

[0059] Example 5

[0060] Different from Example 2, the temperature in step (4) of this example is 180°C.

[0061] Comparative Example 1

[0062] A manganese-based lithium ion sieve is prepared by the following steps:

[0063] (1) LiOH·H2O was used as the lithium source (8 g), commercially available Mn2O3 powder was used as the manganese source (2 g), and ethanol was used as the solvent (the volume fraction of ethanol was 28.57%). The mixture was then transferred to a sealed hydrothermal reactor.

[0064] (2) placing the hydrothermal reactor in an oven at 160° C. for 24 hours, filtering, washing, and drying the reaction product to obtain LiMnO 2 ;

[0065] (3) The LiMnO2 was placed in a muffle furnace, heated to 410°C at a heating rate of 6°C / min, and calcined at 410°C for 4 hours to obtain the precursor product Li 1.6 Mn 1.6 O4 (denoted as LMO);

[0066] (4) the precursor product Li 1.6 Mn 1.6 O4 is acid-leached with hydrochloric acid at a concentration of 0.5 mol / L. The hydrochloric acid reacts with the precursor product E-Li 1.6 Mn 1.6 The ratio of O4 is 200mL:1g, the acid leaching time is 24h, and then the acid leaching product is filtered, washed and dried to obtain manganese-based lithium ion sieve H 1.6 Mn 1.6 O4 (denoted as HMO).

[0067] Comparative Example 2

[0068] Different from Example 2, the temperature in step (4) of this example is 140°C.

[0069] Comparative Example 3

[0070] Different from Example 2, the solvent in step (3) of this example is deionized water.

[0071] Comparative Example 4

[0072] Different from Example 5, the solvent in step (3) of this embodiment is deionized water.

[0073] Because the preparation method described herein uses electrolytic manganese anode mud as raw material, a hazardous solid waste, the leaching toxicity of the synthesized product must be considered. Toxicity testing of the manganese-based lithium ion sieve described herein using the "Solid Waste Leaching Toxicity Leaching Method: Sulfuric Acid and Nitric Acid Method" (HJ / T299-2007) revealed no lead ions leached into the solution. Furthermore, according to the national standard "Hazardous Waste Identification Standard: Leaching Toxicity Identification" (GB 5085.3-2007), the present invention poses no risk of leaching heavy metals into the environment.

[0074] The manganese-based lithium ion sieves prepared in each embodiment and each comparative example were subjected to Li + Adsorption performance test: Specifically, a certain amount of LiOH·H2O was weighed and dissolved in deionized water to prepare Li + The concentration of the simulated brine was 450.54 mg / L (pH = 12.4). At 20 ° C, the manganese-based lithium ion sieve was added as an adsorbent at a dosage of 5 g / L and adsorbed for 24 hours. After the adsorption was completed, the adsorbed mixed solution was filtered through a 0.45 μm microporous membrane and the Li in the filtrate was determined by flame atomic absorption spectrometry. + concentration, and calculate the adsorbent's Li + Adsorption capacity:

[0075]

[0076] Where: Q e is the adsorption capacity, mg / g; C0 is the initial lithium ion concentration, mg / L; C e is the lithium ion concentration after adsorption, mg / L; V is the volume of the solution, L; m is the mass of the ion sieve, g.

[0077] Li + The adsorption performance test results are shown in Table 2:

[0078] Table 2Li + Adsorption performance test results

[0079] Example Adsorption capacity (mg / g) Comparative Example Adsorption capacity (mg / g) Example 1 35.22 Comparative Example 1 30.54 Example 2 40.86 Comparative Example 2 30.12 Example 3 40.25 Comparative Example 3 28.14 Example 4 40.59 Comparative Example 4 32.55 Example 5 39.88 - -

[0080] As shown in Table 2, compared with Example 2, the adsorption capacity of the manganese-based lithium ion sieve prepared using commercially available pure Mn2O3 powder as the manganese source in Comparative Example 1 is not as high as that of the manganese-based lithium ion sieve prepared using electrolytic manganese anode mud as the raw material. The manganese-based lithium ion sieve of the present invention, modified by doping with elements such as Fe, Al, and Pb contained in electrolytic manganese anode mud, increases its adsorption capacity by 33.79% compared to the manganese-based lithium ion sieve prepared using commercially available pure Mn2O3 powder as the manganese source, demonstrating a significant improvement in adsorption performance.

[0081] Comparison of Example 2 of the present invention and Comparative Example 2 shows that when the temperature for the insulation reaction is insufficient, the adsorption energy of the product will be reduced.

[0082] Comparisons between Example 2 and Comparative Example 3, and between Example 5 and Comparative Example 4, show that the product produced using ethanol as the solvent in the present invention exhibits higher adsorption performance than that produced using deionized water. This is because ethanol's chemical properties lower the reaction temperature and allow for more uniform mixing of the raw materials compared to aqueous solutions at the same temperature, resulting in a higher product purity. Using deionized water as the solvent, on the other hand, can lead to incomplete synthesis reactions, resulting in lower purity of the adsorbent product and, consequently, a lower adsorption capacity of the resulting product.

[0083] In addition, the adsorption specific surface area of the manganese-based lithium ion sieve of Example 2 and Comparative Example 1 was tested, wherein the electron microscope image and electron diffraction image before acid leaching activation were as follows: Figure 1 As shown (the surface of the material is observed by electron microscopy, and the change of the crystal plane advantage is observed by electron diffraction pattern), the test results after activation (when using the present invention, E-LMO is activated to obtain E-HMO and then put into use, and is usually stored in the form of E-LMO) are shown in Table 3:

[0084] Table 3 Adsorption specific surface area of manganese-based lithium ion sieve in Example 2 and Comparative Example 1

[0085]

[0086] from Figure 1 As can be seen from Table 3, the use of electrolytic manganese anode mud to prepare Fe, Al, Pb and other doped manganese-based lithium ion sieves is beneficial to change the (111) and (100) crystal plane advantages, and the specific surface area of E-HMO is 64.0082m 2 / g compared with the specific surface area of HMO 89.4981m 2 / g increased by 39.82%, thereby increasing more adsorption sites.

[0087] In addition, the manganese-based lithium ion sieve of the present invention was tested for lithium ion selectivity. Real gas field produced water from a gas field in Sichuan was selected as the lithium extraction solution. The adsorbent was mixed with the real gas field produced water at a dosage of 5g / L at 20°C and adsorbed for 24 hours. After the adsorption was completed, the adsorbed mixture was filtered through a 0.45μm microporous membrane and the Li in the filtrate was determined by flame atomic absorption spectrometry. + 、Na + , K + , Ca 2+ Mg 2+ Concentration, according to, and according to formula (1) calculate the adsorbent Li + 、Na + , K + , Ca 2+ Mg 2+ The adsorption capacity of the ion is then calculated according to the following formula: d To judge the level of selectivity:

[0088]

[0089] The water quality indicators of the actual gas field produced water in this test example are shown in Table 4, and the calculation results of the adsorption capacity and distribution coefficient of the manganese-based lithium ion sieve of Example 2 are shown in Table 5:

[0090] Table 4 Water quality indicators of real gas field produced water

[0091] index pH <![CDATA[Li + (mg / L)]]> <![CDATA[Na + (mg / L)]]> <![CDATA[K + (mg / L)]]> <![CDATA[Ca 2+ (mg / L)]]> <![CDATA[Mg 2+ (mg / L)]]> Numerical 7.25 158.39 28491.93 2026.26 3121.52 311.03

[0092] Table 5 Calculation results of adsorption capacity and distribution coefficient

[0093] ion Adsorption capacity (mg / g) Partition coefficient <![CDATA[Li + ]]> 17.01 231.93 <![CDATA[Na + ]]> 31.05 1.09 <![CDATA[K + ]]> 1.26 0.62 <![CDATA[Ca 2+ ]]> 1.04 0.33 <![CDATA[Mg 2+ ]]> 0.22 0.72

[0094] As can be seen from Table 5, the manganese-based lithium ion sieve of the present invention has the selectivity for each ion in the presence of coexisting ions. + >K + >Na + >Mg 2+ , for Li + Shows good adsorption selectivity.

[0095] The manganese-based lithium ion sieve of the present invention was subjected to a cycle performance test. Specifically, the above adsorption behavior was repeated 7 times, and the lithium ion adsorption capacity and manganese dissolution rate of each cycle were calculated. The test results of Example 2 are shown in Table 6:

[0096] Table 6 Cyclic performance test results

[0097] Number of cycles Adsorption capacity (mg / g) Number of cycles Adsorption capacity (mg / g) 1 17.01 5 16.75 2 17.25 6 16.82 3 16.83 7 16.53 4 16.99 - -

[0098] As can be seen from Table 6, the manganese-based lithium ion sieve of the present invention has excellent cyclability in real water samples, and the adsorption capacity is only reduced by 2.9% after 7 cycles, which is negligible.

[0099] In summary, the present invention can utilize elements such as Fe, Al, and Pb in electrolytic manganese anode mud to dope and modify manganese-based lithium ion sieves, thereby improving their adsorption performance. Compared with the existing technology, the present invention is a significant improvement.

[0100] The above description is merely a representative embodiment of the present invention and does not constitute any form of limitation to the present invention. Any technical personnel familiar with the present invention who, without departing from the scope of the technical solution of the present invention, makes some changes or modifications to the embodiments disclosed above using the technical contents disclosed above are equivalent embodiments of the present invention. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A method for preparing a manganese-based lithium ion sieve based on electrolytic manganese anode mud, characterized in that: The following steps are involved: S1: Obtain electrolytic manganese anode mud, perform high-temperature roasting and reduction on the electrolytic manganese anode mud, and grind it to obtain a Mn2O3 mixture powder 1; S2: mixing acetic acid or acetate solution with the Mn2O3 mixture powder 1, stirring and leaching at a constant temperature, filtering and drying to obtain the Mn2O3 mixture powder 2; S3: Using LiOH·H2O as a lithium source, the Mn2O3 mixture powder as a manganese source, and ethanol as a solvent, the mixture is evenly mixed, sealed, and subjected to heat preservation reaction. The reaction product is filtered, washed, and dried to obtain E-LiMnO2; S4: calcining the E-LiMnO2 at high temperature to obtain the precursor product E-Li 1.6 Mn 1.6 O4; S5: the precursor product E-Li 1.6 Mn 1.6 O4 is acid leached, and then the acid leached product is filtered, washed and dried to obtain manganese-based lithium ion sieve EH 1.6 Mn 1.6 O4.

2. The method for preparing a manganese-based lithium ion sieve based on electrolytic manganese anode mud according to claim 1, characterized in that: In step S1, the high-temperature calcination reduction is performed at a temperature of 750-900° C. and a time of 10-90 minutes.

3. The method for preparing a manganese-based lithium ion sieve based on electrolytic manganese anode mud according to claim 1, characterized in that: In step S2, the concentration of the acetic acid or acetate solution is 1.5-4 mol / L, and the liquid-to-solid ratio during mixing is 8-12 mL:1 g; the constant temperature stirring leaching temperature is 70-90° C., the time is 10-60 min, and the stirring rate is 250-500 rpm.

4. The method for preparing a manganese-based lithium ion sieve based on electrolytic manganese anode mud according to claim 1, characterized in that: In step S3, the mass ratio of the lithium source to the manganese source is 2-8:1, and the volume fraction of the ethanol is 20-80%.

5. The method for preparing a manganese-based lithium ion sieve based on electrolytic manganese anode mud according to claim 1, characterized in that: In step S3, the temperature for the insulation reaction is 140-180° C. and the time is 12-24 hours.

6. The method for preparing a manganese-based lithium ion sieve based on electrolytic manganese anode mud according to claim 1, characterized in that: In step S4, the high-temperature calcination is performed at a temperature of 410-450° C. and a time of 4-8 hours.

7. The method for preparing a manganese-based lithium ion sieve based on electrolytic manganese anode mud according to claim 6, characterized in that: In step S4, when high-temperature calcination is performed, the temperature is increased to the target high-temperature calcination temperature at a heating rate of 6°C / min.

8. The method for preparing a manganese-based lithium ion sieve based on electrolytic manganese anode mud according to claim 1, characterized in that: In step S5, acid leaching is performed using hydrochloric acid.

9. The method for preparing a manganese-based lithium ion sieve based on electrolytic manganese anode mud according to claim 8, characterized in that: The concentration of the hydrochloric acid is 0.2-0.6 mol / L, and the hydrochloric acid reacts with the precursor product E-Li 1.6 Mn 1.6 The ratio of O4 is 200-500mL:1g, and the acid leaching time is 12-36h.

10. A manganese-based lithium ion sieve based on electrolytic manganese anode mud, characterized in that: The manganese-based lithium ion sieve is prepared by the preparation method of the manganese-based lithium ion sieve based on electrolytic manganese anode mud according to any one of claims 1 to 9.

Images