CN114100562A - Doping modified lithium ion sieve and preparation method thereof - Google Patents

Doping modified lithium ion sieve and preparation method thereof Download PDF

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CN114100562A
CN114100562A CN202111337456.3A CN202111337456A CN114100562A CN 114100562 A CN114100562 A CN 114100562A CN 202111337456 A CN202111337456 A CN 202111337456A CN 114100562 A CN114100562 A CN 114100562A
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lithium ion
ion sieve
lithium
manganese
calcination
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海春喜
张果泰
周园
曾金波
申月
孙艳霞
董生德
彭桂萍
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Qinghai Institute of Salt Lakes Research of CAS
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Abstract

The invention discloses a doping modified lithium ion sieve and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving aluminum salt and manganese carbonate in an organic solvent by adopting a sol-gel method, uniformly mixing, and drying to obtain manganese carbonate powder coated with the aluminum salt; subjecting manganese carbonate powder coated with an aluminum salt to a first calcination treatment in an air or oxygen atmosphere to obtain a first calcined product; mixing the first calcined product with lithium hydroxide, grinding, heating and drying to obtain first grinding powder; subjecting the first ground powder to a second calcination treatment in an air or oxygen atmosphere to obtain a second calcined product; mixing the second calcined product with fluoride and then grinding to form second grinding powder; and carrying out third calcination treatment on the second grinding powder in an air atmosphere to obtain the lithium manganese oxide lithium ion sieve codoped and modified by two elements of aluminum and fluorine. The doping modified lithium ion sieve prepared by the invention can reduce the manganese dissolution loss rate of the lithium manganese oxide lithium ion sieve.

Description

Doping modified lithium ion sieve and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion extraction, in particular to a doping modified lithium ion sieve and a preparation method thereof.
Background
Lithium is known as new energy metal in the 21 st century, and has wide application in the fields of new energy materials, medicines, ceramic glass, lithium ion secondary batteries and the like. Lithium resources exist in nature mainly in two forms of solid minerals and liquid deposits, and most of the lithium resources are distributed in brine and seawater. Lithium present in salt lake brine is remarkably characterized by high mg/li ratio, and low concentration of lithium due to very similar properties of mg and li, thereby causing great difficulty in extracting lithium from salt lake brine.
The current methods for extracting lithium from salt lakes are summarized as follows: precipitation, solvent extraction, calcination leaching, nanofiltration, electrodialysis, and adsorption. Compared with other methods, the adsorption method has the advantages of simple process, low cost and environmental protection, can be suitable for extracting lithium from low-grade seawater and brine, and is an ideal method for extracting lithium from solution. The spinel-type lithium manganese oxide ion sieve in the adsorbent material has certain advantages compared with other ion sieve adsorbent materials due to the stable spinel structure and the special three-dimensional tunnel structure, and is particularly characterized by stable structure, high adsorption capacity and good selectivity. The spinel type lithium manganese oxide ion sieve mainly contains LiMnO4、Li1.33Mn1.66O4And Li1.6Mn1.6O4Wherein Li1.6Mn1.6O4Adsorption of (2)Has large capacity and relatively good anti-melting loss performance, and is widely concerned.
Manganese is easily dissolved in the spinel type lithium manganese oxide ionic sieve in the using process, so that the problem of manganese dissolution loss is caused, the adsorption capacity of the ionic sieve is reduced due to the manganese dissolution loss, and the cycle performance of the ionic sieve is also poor. Therefore, how to reduce the manganese dissolution rate of the lithium manganese oxide ion sieve is a problem to be solved.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a doping modified lithium ion sieve and a preparation method thereof, and aims to solve the problem of how to reduce the manganese dissolution loss rate of the lithium manganese oxide lithium ion sieve.
In order to solve the problems, the invention adopts the following technical scheme:
the doped modified lithium ion sieve is a lithium manganese oxide lithium ion sieve which is co-doped and modified by two elements of aluminum and fluorine.
Preferably, the doping-modified lithium ion sieve has the following general formula: li1.6AlxMn1.6-xO4-yFyWherein x is more than or equal to 0.05 and less than or equal to 0.1, and y is more than or equal to 0.05 and less than or equal to 0.3.
Another aspect of the present invention is to provide a method for preparing a doping-modified lithium ion sieve as described above, which comprises the steps of:
s10, dissolving aluminum salt and manganese carbonate in an organic solvent by adopting a sol-gel method, uniformly stirring and mixing, and drying to obtain manganese carbonate powder coated with the aluminum salt;
s20, subjecting the manganese carbonate powder coated with the aluminum salt to first calcination treatment in air or oxygen atmosphere to obtain a first calcined product;
s30, mixing the first calcined product with lithium hydroxide, grinding, heating and drying to obtain first ground powder;
s40, carrying out second calcination treatment on the first ground powder in the air or oxygen atmosphere to obtain a second calcined product;
s50, mixing the second calcined product with fluoride and then grinding to form second grinding powder;
and S60, carrying out third calcination treatment on the second ground powder in an air atmosphere to obtain the lithium manganese oxide lithium ion sieve codoped and modified by aluminum and fluorine.
Preferably, the aluminum salt is C9H21O3Al、AlCl3、Al2(SO4)3Or Al2(SiO3)3The fluoride is NH4F. LiF, NaF or CaF.
Preferably, in the step S10, the aluminum salt and the manganese carbonate are mixed according to a molar ratio of aluminum element to manganese element of 1 (15-31); in step S50, the second calcined product and the fluoride are mixed in a ratio such that the molar ratio of the oxygen element to the fluorine element is (3.95:0.05) to (3.7: 0.3).
Preferably, the calcination temperature of the first calcination treatment in step S20 is 700 ℃ to 950 ℃, and the calcination time is 3h to 6 h.
Preferably, in step S30, the first calcined product and the lithium hydroxide are mixed in a ratio of a molar ratio of lithium element to manganese element of (0.95 to 1.3): 1.
Preferably, the heating and drying in the step S30 is performed at a temperature of 100 ℃ to 150 ℃ for 24h to 48 h.
Preferably, the calcination temperature of the second calcination treatment in step S40 is 400 to 550 ℃, and the calcination time is 3 to 6 hours.
Preferably, the calcination temperature of the third calcination treatment in step S60 is 300 to 500 ℃, and the calcination time is 1 to 4 hours.
The doping modified lithium ion sieve and the preparation method thereof provided by the embodiment of the invention adopt two elements of aluminum and fluorine to dope and modify the lithium manganese oxide lithium ion sieve together, wherein the aluminum element can replace part of trivalent manganese ions, the disorder degree of crystal lattices is improved, and the Jahn-Teller effect of spinel is inhibited, so that Mn is inhibited3+The disproportionation reaction of (2) reduces the dissolution loss of manganese; the introduction of fluorine replaces part of oxygen to combine with manganese to form F-Mn bondThe bond energy is larger than that of an O-Mn bond, so that Mn element is more stable, the dissolution loss of manganese is inhibited, and the structural stability of a lithium ion sieve product is enhanced; on the other hand, the amorphous protective layer composed of aluminum and fluorine is coated on the surface of the lithium manganese oxide lithium ion sieve to isolate and protect the ion sieve material, so that the corrosion of acid and alkali to the ion sieve in the using process is weakened, the dissolution loss of manganese is further reduced, and the cycle stability is improved.
Drawings
FIG. 1 is a process flow diagram of a method of making a lithium ion sieve in an embodiment of the invention;
FIG. 2 is an XRD pattern of a lithium ion sieve product prepared according to example 1 of the present invention;
FIG. 3 is an SEM image of a lithium ion sieve product prepared according to example 1 of the present invention;
FIG. 4 is an XRD pattern of a lithium ion sieve product prepared according to example 2 of the present invention;
FIG. 5 is an SEM image of a lithium ion sieve product prepared according to example 2 of the present invention;
FIG. 6 is an XRD pattern of a lithium ion sieve product prepared according to example 3 of the present invention;
FIG. 7 is an SEM image of a lithium ion sieve product prepared according to example 3 of the present invention;
FIG. 8 is an XRD pattern of a lithium ion sieve product prepared according to example 4 of the present invention;
FIG. 9 is an SEM image of a lithium ion sieve product prepared in example 4 of the present invention.
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. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.
The embodiment of the invention provides a doping modified lithium ion sieve and a preparation method thereof.
The doped modified lithium ion sieve is a lithium manganese oxide lithium ion sieve codoped and modified by aluminum and fluorine. In a preferred embodiment, the doping-modified lithium ion sieve has the following general formula: li1.6AlxMn1.6-xO4-yFyWherein x is more than or equal to 0.05 and less than or equal to 0.1, and y is more than or equal to 0.05 and less than or equal to 0.3.
Referring to fig. 1, the method for preparing the doping-modified lithium ion sieve as described above includes the steps of:
and step S10, dissolving aluminum salt and manganese carbonate in an organic solvent by adopting a sol-gel method, uniformly stirring and mixing, and drying to obtain the manganese carbonate powder coated with the aluminum salt.
In a specific embodiment, the aluminum salt is selected from C9H21O3Al、AlCl3、Al2(SO4)3Or Al2(SiO3)3. The organic solvent is, for example, ethanol.
In a specific scheme, the aluminum salt and the manganese carbonate are mixed according to the molar ratio of the aluminum element to the manganese element of 1 (15-31). It is preferable to mix them in a molar ratio of aluminum element to manganese element of 1: 20.
Step S20, subjecting the manganese carbonate powder coated with the aluminum salt to a first calcination treatment in an air or oxygen atmosphere to obtain a first calcined product.
In a specific scheme, the calcination temperature of the first calcination treatment is 700-950 ℃, and the calcination time is 3-6 h. In a preferred embodiment, the calcination temperature of the first calcination treatment is 800 ℃ and the calcination time is 5 hours.
In step S20, the manganese carbonate powder coated with the aluminum salt is subjected to calcination treatment to obtain a first calcined product of manganese oxide (Mn) mixed with aluminum2O3-Al)。
And S30, mixing the first calcined product with lithium hydroxide, grinding, heating and drying to obtain first ground powder.
In a specific scheme, the first calcined product and the lithium hydroxide are mixed according to the molar ratio of the lithium element to the manganese element of (0.95-1.3): 1. It is preferable to mix them in a molar ratio of 1.05:1 of the lithium element and the manganese element.
In a specific scheme, the heating and drying are carried out for 24-48 h at the temperature of 100-150 ℃. In a preferred scheme, the heating and drying are carried out for 24 hours at the temperature of 120 ℃.
In step S30, the first ground powder obtained by heat drying is a lithium manganese oxide mixed with aluminum, specifically LiMnO2-Al。
And S40, carrying out second calcination treatment on the first ground powder in an air or oxygen atmosphere to obtain a second calcined product.
In a specific scheme, the calcination temperature of the second calcination treatment is 400-550 ℃, and the calcination time is 3-6 h. In a preferred embodiment, the calcination temperature of the second calcination treatment is 450 ℃ and the calcination time is 4 h.
In step S40, the first ground powder is calcined to obtain a second calcined product which is an aluminum-doped manganese oxide, specifically Li1.6AlxMn1.6-xO4Wherein x is more than or equal to 0.05 and less than or equal to 0.1.
And S50, mixing the second calcined product with fluoride and grinding to form second grinding powder.
In a specific embodiment, the fluoride may be selected from NH4F. LiF, NaF or CaF.
In a specific embodiment, the second calcined product and the fluoride are mixed in a ratio of (3.95:0.05) to (3.7:0.3) in terms of the molar ratio of the oxygen element to the fluorine element.
And S60, carrying out third calcination treatment on the second ground powder in an air atmosphere to obtain the lithium manganese oxide lithium ion sieve codoped and modified by aluminum and fluorine.
In a specific scheme, the calcining temperature of the third calcining treatment is 300-500 ℃, and the calcining time is 1-4 h. In a preferred embodiment, the calcination temperature of the second calcination treatment is 400 ℃ and the calcination time is 2 hours.
In step S60, the second ground powder is subjected to calcination treatment to obtain a second calcined product which is an aluminum-and fluorine-doped manganese oxide, specifically Li1.6AlxMn1.6-xO4-yFyWherein x is more than or equal to 0.05 and less than or equal to 0.1, and y is more than or equal to 0.05 and less than or equal to 0.3.
The doping modified lithium ion sieve and the preparation method thereof provided in the above embodiments adopt two elements of aluminum and fluorine to dope and modify the lithium manganese oxide lithium ion sieve together, wherein the aluminum element can replace part of trivalent manganese ions, improve the degree of disorder of crystal lattices, and inhibit the Jahn-Teller effect of spinel, thereby inhibiting Mn3+The disproportionation reaction of (2) reduces the dissolution loss of manganese; the introduction of the fluorine element replaces partial oxygen element to combine with manganese to form an F-Mn bond, and the bond energy of the F-Mn bond is larger than that of an O-Mn bond, so that the Mn element is more stable, the dissolution loss of the manganese is inhibited, and the structural stability of the lithium ion sieve product is enhanced; on the other hand, the amorphous protective layer composed of aluminum and fluorine is coated on the surface of the lithium manganese oxide lithium ion sieve to isolate and protect the ion sieve material, so that the corrosion of acid and alkali to the ion sieve in the using process is weakened, the dissolution loss of manganese is further reduced, and the cycle stability is improved.
Example 1
(1) And adopting a sol-gel method, wherein the molar ratio of Al to Mn is 1:20 ratio of C to C9H21O3Al and MnCO3Dissolving in ethanol, stirring, mixing, and drying.
(2) And (2) placing the powder dried in the step (1) in a calcining furnace, introducing air, controlling the heating rate to be 5 ℃/min, heating to 800 ℃, and calcining for 5 hours at the temperature of 800 ℃.
(3) And (3) mixing the calcined product obtained in the step (2) with lithium hydroxide according to a molar ratio of Li to Mn of 1.05:1, grinding, and then heating at the temperature of 120 ℃ for 24 hours for drying treatment.
(4) And (3) placing the product dried in the step (3) in a calcining furnace, introducing air, controlling the heating rate to be 5 ℃/min, heating to 450 ℃, and calcining for 5 hours at the temperature of 450 ℃.
(5) Reacting the calcined product of step (4) with NH4F according to the molar ratio of O to F of 3.95: mixing at a ratio of 0.05, and grinding.
(6) And (3) placing the ground product obtained in the step (5) in a calcining furnace, introducing air, controlling the heating rate to be 5 ℃/min, heating to 400 ℃, calcining for 2 hours at the temperature of 400 ℃, naturally cooling, and collecting a sample to obtain a doped modified lithium ion sieve product 1.
The lithium ion sieve product 1 obtained in this example was subjected to X-ray diffraction (abbreviated as XRD) and scanning electron microscope (abbreviated as SEM) tests, respectively, to obtain an XRD spectrum of fig. 2 and an SEM spectrum of fig. 3.
According to the XRD pattern shown in FIG. 2, the XRD pattern of lithium ion sieve product 1 showed no appearance of hetero-peaks in comparison with that of standard card (JCPDS card No.52-1841), and remained the same as that of Li1.6Mn1.6O4The same characteristic peak proves that the introduction of Al and F does not generate a hetero phase, and the Al and F still belong to a spinel Fd-3m space group with a lattice parameter of
Figure BDA0003345213260000061
According to the SEM image shown in fig. 3, the lithium ion sieve product 1 obtained in this example had irregular spherical-like morphology and particle size of micrometer scale.
Example 2
Example 2 differs from example 1 in that: in the step (5), the calcined product of the step (4) is reacted with NH4F according to the molar ratio of O to F of 3.95: mixing at a ratio of 0.1, and grinding. The remaining process steps of example 2 are identical to those of example 1 and are therefore not described in detail.
This example was prepared to obtain a doped modified lithium ion sieve product 2.
The lithium ion sieve product 2 obtained in this example was subjected to XRD testing and SEM testing, respectively, to obtain an XRD pattern of fig. 4 and an SEM pattern of fig. 5.
According to the XRD pattern shown in FIG. 4, the lithium ion sieve product 2 of this example still retained Li1.6Mn1.6O4Same asCharacteristic peak, compared with the lithium ion sieve product 1 of example 1, no hetero-phase appears, the lattice parameter is slightly reduced, that is
Figure BDA0003345213260000071
According to the SEM image shown in FIG. 5, the lithium ion sieve product 2 obtained in this example has a material morphology which is not greatly changed, and is still in an irregular sphere-like shape and has a size which is not significantly changed, compared with the lithium ion sieve product 1 in example 1.
Example 3
Example 3 differs from example 1 in that: in the step (5), the calcined product of the step (4) is reacted with NH4F, according to the molar ratio of O to F, of 3.8: mixing at a ratio of 0.2, and grinding. The remaining process steps of example 3 are identical to those of example 1 and are therefore not described in detail.
This example was prepared to obtain a doped modified lithium ion sieve product 3.
The lithium ion sieve product 3 obtained in this example was subjected to XRD testing and SEM testing, respectively, to obtain an XRD pattern of fig. 6 and an SEM pattern of fig. 7.
According to the XRD pattern shown in FIG. 6, lithium ion sieve product 3 of this example showed no appearance of a hetero peak and the main phase remained spinel type Li1.6Mn1.6O4Further decrease of the lattice parameter compared to the products of example 1 and example 2.
According to the SEM image shown in FIG. 7, the morphology of the lithium ion sieve product 3 obtained in this example is still irregular spheroidal, but it can be seen that the particle agglomeration is severe, and the size is slightly increased compared with the products of examples 1 and 2.
Example 4
Example 4 differs from example 1 in that: in the step (5), the calcined product of the step (4) is reacted with NH4F, according to the molar ratio of O to F, of 3.7: mixing at a ratio of 0.3, and grinding. The remaining process steps of example 4 are identical to those of example 1 and are therefore not described in detail.
This example was prepared to obtain a doped modified lithium ion sieve product 4.
The lithium ion sieve product 4 obtained in this example was subjected to XRD testing and SEM testing, respectively, to obtain an XRD pattern of fig. 8 and an SEM pattern of fig. 9.
According to the XRD pattern shown in fig. 8, the lithium ion sieve product 4 of this example still well maintains the spinel phase structure, and the lattice parameter is further reduced.
According to the SEM image shown in FIG. 9, the lithium ion sieve product 4 obtained in the present example still has an irregular spherical-like shape, and the size of the product is further increased.
Example 5
Example 5 differs from example 1 in that: in the step (1), AlCl is used3By replacing C in example 1 by an aluminium salt9H21O3Al; in step (5), LiF was used as fluoride in place of NH in example 14F. The remaining process steps of example 5 are identical to those of example 1 and are therefore not described in detail.
This example was prepared to obtain a doped modified lithium ion sieve product 5.
Example 6
Example 6 differs from example 1 in that: in the step (1), Al is used2(SO4)3By replacing C in example 1 by an aluminium salt9H21O3Al; in step (5), NaF was used as a fluoride in place of NH in example 14F. The remaining process steps of example 6 are identical to those of example 1 and are therefore not described in detail.
This example was prepared to obtain a doped modified lithium ion sieve product 6.
Example 7
Example 7 differs from example 1 in that: in the step (1), Al is used2(SiO3)3By replacing C in example 1 by an aluminium salt9H21O3Al; in step (5), CaF is used2By substitution of NH in example 1 for fluoride4F. The remaining process steps of example 7 are identical to those of example 1 and are therefore not described in detail.
This example was prepared to obtain a doped modified lithium ion sieve product 7.
Comparative example 1
Comparative example 1 is different from example 1 in that: in the step (1), C is not added9H21O3Al; in the step (5), NH is not added4F. The remaining process steps and process conditions of comparative example 1 were exactly the same as those of example 1, i.e., comparative example 1 prepared an undoped modified lithium ion sieve product, designated as comparative example 1.
Comparative example 2
Comparative example 2 differs from example 1 in that: in the step (5), NH is not added4F. The remaining process steps and process conditions of comparative example 2 were exactly the same as those of example 1, i.e., comparative example 2 prepared a lithium ion sieve product modified by doping with only aluminum element, and designated as comparative example 2.
Comparative example 3
Comparative example 3 differs from example 1 in that: in the step (1), C is not added9H21O3And Al. The remaining process steps and process conditions of comparative example 3 are exactly the same as those of example 1, i.e., comparative example 3 prepares a lithium ion sieve product modified by doping only with fluorine, and is designated as comparative example 3.
And (3) testing the adsorption capacity:
the lithium ion sieve products 1 to 7 of examples 1 to 7 and the comparative products 1 to 3 of comparative examples 1 to 3, which were equal in volume, were each subjected to lithium adsorption on a lithium-containing solution of equal concentration, shaken at room temperature for 24 hours, and the ion concentration in the supernatant test solution was taken and the adsorption capacity was calculated. And (3) continuously using each lithium ion sieve product after adsorption after lithium is removed by the acid solution, continuously placing the lithium ion sieve product in a lithium-containing solution for adsorbing lithium, and testing the adsorption capacity after the lithium ion sieve product is circularly used for five times.
The adsorption amount of the first adsorption and the adsorption amount of the fifth adsorption in the cycle are summarized in the following table 1.
Table 1:
first adsorption Capacity (mg/g) Fifth adsorption Capacity (mg/g)
Lithium ion sieve product 1 33.56 29.97
Lithium ion sieve product 2 31.14 26.83
Lithium ion sieve product 3 30.42 26.88
Lithium ion sieve product 4 30.80 26.97
Lithium ion sieve product 5 29.93 25.42
Lithium ion sieve product 6 30.20 26.43
Lithium ion sieve product 7 29.87 25.45
Comparative product 1 27.60 23.36
Comparative product 2 29.54 23.96
Comparative product 3 28.83 24.45
From the data in table 1, it can be seen that: compared with the unmodified lithium ion sieve product doped with the aluminum or fluorine single element in the comparative example, the first adsorption capacity of the aluminum and fluorine co-doped modified lithium ion sieve product prepared by the invention is greatly increased, and after multiple times of cyclic adsorption, the adsorption capacity is still obviously higher than that of the lithium ion sieve product in the comparative example, so that the lithium ion sieve prepared by the embodiment of the invention has good adsorption performance.
Manganese dissolution loss rate test:
the lithium ion sieve products 1 to 7 of examples 1 to 7 and the comparative products 1 to 3 of comparative examples 1 to 3, which were equal in volume, were each subjected to lithium adsorption on a lithium-containing solution of equal concentration, shaken at room temperature for 24 hours, and the ion concentration in the supernatant test solution was taken and the adsorption capacity was calculated. After lithium is removed from each lithium ion sieve product after adsorption through an acid solution, a supernatant is taken to measure the ion concentration in the solution, the manganese dissolution loss rate is calculated, and the test results are shown in the following table 2.
Table 2:
dissolution loss ratio (%) of manganese
Lithium ion sieve product 1 1.56
Lithium ion sieve product 2 1.61
Lithium ion sieve product 3 1.75
Lithium ion sieve product 4 1.81
Lithium ion sieve product 5 1.76
Lithium ion sieve product 6 1.74
Lithium ion sieve product 7 1.75
Comparative product 1 2.26
Comparative product 2 2.09
Comparative product 3 1.95
From the data in table 2, it can be seen that: compared with the lithium ion sieve product which is not doped in the comparative example and is doped by the aluminum or fluorine single element, the manganese dissolution rate of the aluminum and fluorine co-doped modified lithium ion sieve product prepared by the invention is obviously reduced, and the lithium ion sieve product prepared by the embodiment of the invention has better stability and can be used for long-term cycle use.
The foregoing is directed to embodiments of the present application and it is noted that numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.

Claims (10)

1. The doped modified lithium ion sieve is characterized in that the doped modified lithium ion sieve is a lithium manganese oxide lithium ion sieve which is co-doped and modified by aluminum and fluorine.
2. The doping-modified lithium ion sieve of claim 1, wherein the doping-modified lithium ion sieve has the general formula: li1.6AlxMn1.6-xO4-yFyWherein x is more than or equal to 0.05 and less than or equal to 0.1, and y is more than or equal to 0.05 and less than or equal to 0.3.
3. A method of preparing a doping-modified lithium ion sieve as claimed in claim 1 or 2, comprising the steps of:
s10, dissolving aluminum salt and manganese carbonate in an organic solvent by adopting a sol-gel method, uniformly stirring and mixing, and drying to obtain manganese carbonate powder coated with the aluminum salt;
s20, subjecting the manganese carbonate powder coated with the aluminum salt to first calcination treatment in air or oxygen atmosphere to obtain a first calcined product;
s30, mixing the first calcined product with lithium hydroxide, grinding, heating and drying to obtain first ground powder;
s40, carrying out second calcination treatment on the first ground powder in the air or oxygen atmosphere to obtain a second calcined product;
s50, mixing the second calcined product with fluoride and then grinding to form second grinding powder;
and S60, carrying out third calcination treatment on the second ground powder in an air atmosphere to obtain the lithium manganese oxide lithium ion sieve codoped and modified by aluminum and fluorine.
4. The method of claim 3, wherein the aluminum salt is C9H21O3Al、AlCl3、Al2(SO4)3Or Al2(SiO3)3The fluoride is NH4F. LiF, NaF or CaF2。
5. The method of claim 3, wherein in step S10, the aluminum salt and the manganese carbonate are mixed in a molar ratio of aluminum element to manganese element of 1: (15-31); in step S50, the second calcined product and the fluoride are mixed in a molar ratio of the oxygen element to the fluorine element of (3.95:0.05) to (3.7: 0.3).
6. The method for preparing a lithium ion sieve according to claim 3, wherein the calcination temperature of the first calcination treatment in the step S20 is 700 ℃ to 950 ℃, and the calcination time is 3h to 6 h.
7. The method of claim 3, wherein in step S30, the first calcined product and the lithium hydroxide are mixed in a molar ratio of lithium element to manganese element of (0.95-1.3) to 1.
8. The method of claim 3, wherein the heating and drying in the step S30 is performed at a temperature of 100 to 150 ℃ for 24 to 48 hours.
9. The method for preparing a lithium ion sieve according to claim 3, wherein the calcination temperature of the second calcination treatment in the step S40 is 400 to 550 ℃, and the calcination time is 3 to 6 hours.
10. The method for preparing a lithium ion sieve according to claim 3, wherein the calcination temperature of the third calcination treatment in the step S60 is 300 to 500 ℃, and the calcination time is 1 to 4 hours.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101961634A (en) * 2010-09-16 2011-02-02 中南大学 Manganese series lithium ion sieve adsorbent and preparation method of precursor thereof
CN109529757A (en) * 2018-12-05 2019-03-29 上海空间电源研究所 A kind of preparation method of the long-life lithium ion sieve adsorbant of surface doping
KR20200141653A (en) * 2019-06-11 2020-12-21 주식회사 셀젠 Enriching method of lithium using adsorbent
CN112678875A (en) * 2020-12-25 2021-04-20 中国科学院青海盐湖研究所 Spinel type Li1.6Mn1.6O4Preparation method of microsphere powder

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101961634A (en) * 2010-09-16 2011-02-02 中南大学 Manganese series lithium ion sieve adsorbent and preparation method of precursor thereof
CN109529757A (en) * 2018-12-05 2019-03-29 上海空间电源研究所 A kind of preparation method of the long-life lithium ion sieve adsorbant of surface doping
KR20200141653A (en) * 2019-06-11 2020-12-21 주식회사 셀젠 Enriching method of lithium using adsorbent
CN112678875A (en) * 2020-12-25 2021-04-20 中国科学院青海盐湖研究所 Spinel type Li1.6Mn1.6O4Preparation method of microsphere powder

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GUOTAI ZHANG ET AL.: "Synthesis of aluminum-doped ion-sieve manganese oxides powders with enhanced adsorption performance", COLLOIDS AND SURFACES A, pages 2 *
GUOTAI ZHANG ET AL: "Improved structural stability and adsorption capacity of adsorbent material Li1.6Mn1.6O4 via facile surface fluorination", COLLOIDS AND SURFACES A: PHYSICOCHEMICAL AND ENGINEERING ASPECTS, pages 2 *

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