CN114259976A - Preparation method of modified manganese-based lithium ion sieve - Google Patents
Preparation method of modified manganese-based lithium ion sieve Download PDFInfo
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Abstract
The invention discloses a preparation method of a modified manganese-based lithium ion sieve, which comprises the following steps: s01: mixing and grinding lithium salt and manganese oxide, placing the mixture into a homogeneous reactor for reaction for 24-48 h, and drying and grinding the product after the reaction is finished to obtain LiMnO2Powder; s02: mixing the LiMnO2Calcining the powder at the temperature of 300-1.6Mn1.6O4Powder; s03: subjecting the Li to1.6Mn1.6O4Powder with NH4F, mixing and grinding, putting into a homogeneous reactor, keeping the rotating speed of the homogeneous reactor at 1-5 rpm, controlling the reaction temperature at 100-300 ℃ and the reaction time at 1-4 h; obtaining modified powder; s04: acidizing the modified powder in inorganic acid for 12-24 h; after acidizing, centrifugal drying is carried out to obtain the modified manganeseBased lithium ion sieves. The modified manganese-based lithium ion sieve obtained by the method can effectively reduce the dissolution loss of manganese.
Description
Technical Field
The invention relates to the field of lithium ion sieves, in particular to a preparation method of a modified manganese-based lithium ion sieve.
Background
Lithium is an important element in modern energy development, has been widely applied to various fields such as new energy and the like, is an indispensable raw material for a lithium battery with high specific energy density, and in recent years, with the continuous development of industries such as new energy automobiles, power grid energy storage, portable electronic equipment and the like, the demand of the lithium battery is increased explosively, so that the market demand of the lithium resource in the world is increased continuously.
Lithium resources exist mainly in two forms: one is lithium-containing ores such as lepidolite, spodumene, laponite; and secondly, lithium-containing water resources, such as salt lakes and underground water, have more than 60 percent of lithium resources existing in the salt lakes globally, so that the lithium resources in the salt lakes become important sources for the development of industries such as lithium batteries and the like. Among the technologies for extracting lithium from salt lakes, the adsorption method has been widely used because of its superiority over other methods in extracting lithium from salt lakes with high magnesium-lithium ratio, in which a lithium ion sieve for the adsorption process is widely spotlighted due to its characteristics of high selectivity to lithium ions, high adsorption capacity, low toxicity and low cost, among which Li is widely used1.6Mn1.6O4The adsorption capacity is most representative from the viewpoint of higher theoretical adsorption capacity and better stability after multiple cycles.
Despite Li1.6Mn1.6O4The theoretical adsorption capacity is higher, but the manganese loss is still larger during the adsorption and desorption processes, which can continuously reduce the adsorption capacity of the ionic sieve during the circulation process and influence the stability of the ionic sieve structure.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the problems in the related art. Therefore, the invention aims to provide a preparation method of a modified manganese-based lithium ion sieve, and the obtained modified manganese-based lithium ion sieve can effectively reduce the dissolution loss of manganese.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a modified manganese-based lithium ion sieve comprises the following steps:
s01: mixing and grinding lithium salt and manganese oxide, placing the mixture into a homogeneous reactor for reaction for 24-48 h, and drying and grinding the product after the reaction is finished to obtain LiMnO2Powder;
s02: mixing the LiMnO2Calcining the powder at the temperature of 300-1.6Mn1.6O4Powder;
s03: subjecting the Li to1.6Mn1.6O4Powder with NH4F, mixing and grinding, putting into a homogeneous reactor, keeping the rotating speed of the homogeneous reactor at 1-5 rpm, controlling the reaction temperature at 100-300 ℃ and the reaction time at 1-4 h; obtaining modified powder;
s04: acidizing the modified powder in inorganic acid for 12-24 h; and after acidification treatment, centrifugal drying is carried out to obtain the modified manganese-based lithium ion sieve.
Further, in the step S01, the rotating speed of the homogeneous reactor is kept to be 1-5 r/m, and the reaction temperature is 100-150 ℃.
Further, in step S01, Mn is used as the manganese oxide2O3。
Further, the lithium salt is LiOH H2O、LiOH、Li2CO3Any one of the above.
Furthermore, the molar ratio of Li/Mn in the lithium salt and the manganese oxide in the step S01 is 1.0-1.3: 1.
Further, Li in the step S031.6Mn1.6O4The molar ratio of the powder to O/F in NH4F is 4: 0.05-0.3.
Further, the inorganic acid is any one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
Further, the concentration of the inorganic acid is 0.1-1 mol/L, and the soaking time is 12-24 h.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the advantages thatHas the following advantages: in the invention, Li1.6Mn1.6O4Powder with NH4F is mixed and ground and put into a homogeneous reactor for reaction, and F ions replace Li in the reaction process1.6Mn1.6O4Part of O in the powder enhances the electronegativity and the crystal lattice contraction of the modified manganese-based lithium ion sieve, thereby improving the adsorption capacity, reducing the dissolution loss of manganese and enhancing the cycle performance of the lithium ion sieve; the method of the invention can be manufactured and applied in large scale.
Drawings
FIG. 1 is an XRD (X-ray diffraction) pattern of the modified manganese-based lithium ion sieve in example 1;
FIG. 2 is an SEM image and an EDS Mapping fluorine distribution diagram of the modified manganese-based lithium ion sieve in example 1;
FIG. 3 is a graph showing a particle size distribution of the modified manganese-based lithium ion sieve of example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings.
A preparation method of a modified manganese-based lithium ion sieve comprises the following steps:
s01: mixing and grinding lithium salt and manganese oxide, putting the mixture into a homogeneous reactor for reaction for 24-48 h, keeping the rotating speed of the homogeneous reactor at 1-5 r/min, and controlling the reaction temperature at 100-150 ℃. After the reaction is finished, drying and grinding the product to obtain LiMnO2Powder; wherein the manganese oxide is Mn2O3. The lithium salt is LiOH. H2O、LiOH、Li2CO3Any one of (a); and the molar ratio of Li/Mn in the lithium salt and the manganese oxide is 1.0-1.3: 1.
S02: mixing LiMnO2Calcining the powder at the temperature of 300-1.6Mn1.6O4Powder;
s03: mixing Li1.6Mn1.6O4Powder with NH4F, mixing and grinding, putting into a homogeneous reactor, keeping the rotating speed of the homogeneous reactor at 1-5 rpm, and reacting at 100-300 DEG CThe time is 1-4 h; obtaining modified powder; li1.6Mn1.6O4The molar ratio of the powder to O/F in NH4F is 4: 0.05-0.3.
S04: acidizing the modified powder in inorganic acid for 12-24 h; and after acidification treatment, centrifugal drying is carried out to obtain the modified manganese-based lithium ion sieve. Wherein the inorganic acid is any one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; the concentration of the inorganic acid is 0.1-1 mol/L, and the soaking time is 12-24 h.
In step S03, Li1.6Mn1.6O4Powder with NH4F is mixed and ground and put into a homogeneous reactor for reaction, and during the reaction, F ions replace Li1.6Mn1.6O4Part of O in the powder enhances the electronegativity and the crystal lattice contraction of the modified manganese-based lithium ion sieve, thereby improving the adsorption capacity, reducing the dissolution loss of manganese and enhancing the cycle performance of the lithium ion sieve; the method of the invention can be manufactured and applied in large scale.
The present application is further illustrated by the following examples and comparative examples:
example 1
A preparation method of a modified manganese-based lithium ion sieve comprises the following steps:
s01: reacting LiOH & H2O and Mn2O3Mixing and grinding, putting into a homogeneous reactor, wherein the rotating speed of the reactor is 5 r/min, the reaction temperature is 130 ℃, and the reaction time is 24 h; after the reaction is finished, drying and grinding the product to obtain LiMnO2Powder; wherein, LiOH. H2O and Mn2O3The molar ratio of the Li to the Mn is 1.2: 1;
s02: the LiMnO prepared in the previous step2Calcining the powder at 350 ℃ for 8 hours to obtain Li1.6Mn1.6O4Powder;
s03: li prepared in the previous step1.6Mn1.6O4Powder with NH4F mixed grinding, wherein Li1.6Mn1.6O4Powder with NH4The molar ratio of O to F in F is 4:0.2, putting the mixture into a homogeneous reactor, and reactingThe rotating speed of the reactor is 5 r/min, the reaction temperature is 150 ℃, and the reaction time is 4 h; obtaining modified powder;
s04: acidizing the modified powder prepared in the previous step in 0.5mol/L hydrochloric acid for 24 hours; and after acidification treatment, centrifugal drying is carried out to obtain the modified manganese-based lithium ion sieve.
Fig. 1 is an XRD spectrum of the modified manganese-based lithium ion sieve in example 1, which shows that the finally obtained modified manganese-based lithium ion sieve maintains good crystallinity and the crystal structure is not significantly changed.
Fig. 2 is an SEM image and an EDS Mapping fluorine distribution diagram of the modified manganese-based lithium ion sieve in example 1, and it can be seen that the distribution of fluorine in the finally obtained modified manganese-based lithium ion sieve particles is relatively uniform.
FIG. 3 is a particle size distribution diagram of the modified manganese-based lithium ion sieve in example 1, and it can be seen that the finally obtained modified manganese-based lithium ion sieve has a uniform particle size and is substantially maintained at D50＝9.677μm。
Example 2
A preparation method of a modified manganese-based lithium ion sieve comprises the following steps:
s01: mixing LiOH and Mn2O3Mixing and grinding, putting into a homogeneous reactor, wherein the rotating speed of the reactor is 5 r/min, the reaction temperature is 130 ℃, and the reaction time is 24 h; after the reaction is finished, drying and grinding the product to obtain LiMnO2Powder; wherein, LiOH and Mn2O3The molar ratio of the Li to the Mn is 1.0: 1;
s02: the LiMnO prepared in the previous step2Calcining the powder at 350 ℃ for 8 hours to obtain Li1.6Mn1.6O4Powder;
s03: li prepared in the previous step1.6Mn1.6O4Powder with NH4F mixed grinding, wherein Li1.6Mn1.6O4Powder with NH4The molar ratio of O to F in F is 4:0.1, the mixture is put into a homogeneous reactor, the rotating speed of the reactor is 5 r/min, the reaction temperature is 150 ℃, and the reaction time is 4 hours; obtaining modified powder;
s04: acidizing the modified powder prepared in the previous step in 0.5mol/L sulfuric acid for 24 hours; and after acidification treatment, centrifugal drying is carried out to obtain the modified manganese-based lithium ion sieve.
Example 3
A preparation method of a modified manganese-based lithium ion sieve comprises the following steps:
s01: mixing Li2CO3And Mn2O3Mixing and grinding, putting into a homogeneous reactor, wherein the rotating speed of the reactor is 5 r/min, the reaction temperature is 130 ℃, and the reaction time is 24 h; after the reaction is finished, drying and grinding the product to obtain LiMnO2Powder; wherein Li2CO3And Mn2O3The molar ratio of the Li to the Mn is 1.3: 1;
s02: the LiMnO prepared in the previous step2Calcining the powder at 350 ℃ for 8 hours to obtain Li1.6Mn1.6O4Powder;
s03: li prepared in the previous step1.6Mn1.6O4Powder with NH4F mixed grinding, wherein Li1.6Mn1.6O4Powder with NH4The molar ratio of O to F in F is 4:0.05, the mixture is put into a homogeneous reactor, the rotating speed of the reactor is 5 r/min, the reaction temperature is 150 ℃, and the reaction time is 4 hours; obtaining modified powder;
s04: acidizing the modified powder prepared in the previous step in 0.5mol/L nitric acid for 24 hours; and after acidification treatment, centrifugal drying is carried out to obtain the modified manganese-based lithium ion sieve.
Comparative example 1
S01: same as step S01 in embodiment 1;
s02: same as step S02 in embodiment 1;
s03: acidizing the powder prepared in the previous step in 0.5mol/L hydrochloric acid for 24 hours; and after acidification treatment, centrifugal drying is carried out to obtain the manganese-based lithium ion sieve.
Comparative example 2
A preparation method of a modified manganese-based lithium ion sieve comprises the following steps:
s01: same as step S01 in embodiment 1;
s02: will be the previous stepPrepared LiMnO2Powder with NH4F mixed grinding, wherein Li1.6Mn1.6O4Powder with NH4The molar ratio of O to F in F is 4:0.2, the mixture is put into a homogeneous reactor, the rotating speed of the reactor is 5 r/min, the reaction temperature is 150 ℃, and the reaction time is 4 hours; obtaining modified powder;
s03: the same as step S04 in embodiment 1.
Experimental example 1
20mL of brine having an initial lithium ion concentration of 165mg/L and a pH of the solution of 12.0 were added to each of the coated lithium ion sieves of examples 1 to 3 and comparative examples 1 to 2 in an amount of 0.1g, and the adsorption capacities thereof were measured at 25 ℃ for 24 hours as shown in Table 1.
The lithium ion sieves of examples 1 to 3 and comparative examples 1 to 2 were tested for manganese dissolution loss by the following method: 0.1g of the lithium ion sieves of examples 1 to 3 and comparative examples 1 to 2 was weighed into 20ml of a Li-containing material+Absorbing the lithium ion sieve in 165mg/L salt lake brine at 25 ℃ for 48 hours, then carrying out acid washing on the lithium ion sieve, taking supernate after the acid washing process, and testing residual Mn by using an atomic absorption spectrometer or ICP (inductively coupled plasma)2+The concentration of (c); the test results are shown in table 1.
TABLE 1 adsorption capacity and manganese dissolution loss of lithium ion sieves of various examples and comparative examples
| Adsorption capacity (mg/g) | Manganese dissolution loss (%) | |
| Example 1 | 31.0 | 0.20 |
| Example 2 | 29.1 | 0.22 |
| Example 3 | 29.3 | 0.20 |
| Comparative example 1 | 27.8 | 0.23 |
| Comparative example 2 | 28.5 | 0.28 |
It can be seen that: compared with the comparative example 1, the modified manganese-based lithium ion sieve in the example 1 has the adsorption capacity improved by 11.5 percent, and the manganese dissolution loss reduced by 13.0 percent. The adsorption capacity of the modified manganese-based lithium ion sieve in the embodiment 2 is improved by 4.7%, and the manganese dissolution loss is reduced by 4.3%. The adsorption capacity of the modified manganese-based lithium ion sieve in the embodiment 3 is improved by 5.4%, and the manganese dissolution loss is reduced by 13.0%.
Although the modified manganese-based lithium ion sieve of comparative example 2 improved the adsorption capacity by 2.5%, the manganese dissolution loss was also improved by 21.7% as compared with comparative example 1, because of LiMnO2Powder with NH4In the direct mixing reaction process of F, the modification affects the formation of the bulk structure, and the effect of reducing the manganese dissolution loss in examples 1 to 3 cannot be obtained.
Therefore, the modified manganese-based lithium ion sieve obtained in a specific manner in the application has F ions replacing Li in the modification process1.6Mn1.6O4Part of O in the powder enhances the electronegativity of the modified manganese-based lithium ion sieve and shrinks the crystal lattice, thereby improving the adsorption capacity, reducing the dissolution loss of manganese and enhancing the cycle performance of the lithium ion sieve.
The above description is only a preferred embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, so that all equivalent structural changes made by using the contents of the specification and the drawings of the present invention should be included in the scope of the appended claims.
Claims (8)
1. The preparation method of the modified manganese-based lithium ion sieve is characterized by comprising the following steps of:
s01: mixing and grinding lithium salt and manganese oxide, placing the mixture into a homogeneous reactor for reaction for 24-48 h, and drying and grinding the product after the reaction is finished to obtain LiMnO2Powder;
s02: mixing the LiMnO2Calcining the powder at the temperature of 300-1.6Mn1.6O4Powder;
s03: subjecting the Li to1.6Mn1.6O4Powder with NH4F, mixing and grinding, putting into a homogeneous reactor, keeping the rotating speed of the homogeneous reactor at 1-5 rpm, controlling the reaction temperature at 100-300 ℃ and the reaction time at 1-4 h; obtaining modified powder;
s04: acidizing the modified powder in inorganic acid for 12-24 h; and after acidification treatment, centrifugal drying is carried out to obtain the modified manganese-based lithium ion sieve.
2. The method of claim 1, wherein in step S01, the rotation speed of the homogeneous reactor is maintained at 1-5 rpm, and the reaction temperature is maintained at 100-150 ℃.
3. The method of claim 1, wherein the manganese oxide in step S01 is Mn2O3。
4. The method of claim 1, wherein the lithium salt is LiOH-H2O、LiOH、Li2CO3In (1)One kind of the medicine.
5. The method for preparing the modified manganese-based lithium ion sieve of claim 1, wherein the molar ratio of Li/Mn in the lithium salt and the manganese oxide in step S01 is 1.0-1.3: 1.
6. The method of claim 1, wherein Li in the step S03 is selected from Li, n1.6Mn1.6O4The molar ratio of the powder to O/F in NH4F is 4: 0.05-0.3.
7. The method for preparing the modified manganese-based lithium ion sieve of claim 1, wherein the inorganic acid is any one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
8. The preparation method of the modified manganese-based lithium ion sieve of claim 7, wherein the concentration of the inorganic acid is 0.1-1 mol/L, and the soaking time is 12-24 h.
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