CN112678875B - Spinel type Li 1.6 Mn 1.6 O 4 Preparation method of microsphere powder - Google Patents
Spinel type Li 1.6 Mn 1.6 O 4 Preparation method of microsphere powder Download PDFInfo
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Abstract
The invention discloses spinel type Li 1.6 Mn 1.6 O 4 The preparation method of the microsphere powder comprises the following steps: preparing soluble aluminum salt and soluble manganese salt to form a mixed salt solution; preparing a precipitator solution containing carbonate ions, adding the precipitator solution into a mixed salt solution for precipitation reaction, performing solid-liquid separation, and washing and drying a solid-phase product to obtain a first powder product containing manganese carbonate; roasting the first powder product to obtain a second powder product containing manganese oxide; mixing the second powder product with lithium salt powder to form mixed powder, sequentially carrying out first-stage roasting and second-stage roasting on the mixed powder, and cooling to obtain the spinel type Li 1.6 Mn 1.6 O 4 Microsphere powder; the first stage roasting is carried out in inert gas atmosphere, the second stage roasting is carried out in oxygen atmosphere, and the roasting temperature of the first stage roasting is higher than that of the second stage roasting. The method of the invention can prepare Li with low impurity content and micron-nanometer size 1.6 Mn 1.6 O 4 Spherical powder.
Description
Technical Field
The invention belongs to the technical field of lithium resource extraction, and relates to manganese ion sieve MnO 2 ·0.5H 2 Precursor material of OA preparation method of the material, in particular to spinel type Li 1.6 Mn 1.6 O 4 A preparation method of microsphere powder.
Background
In recent years, with the rapid development of electric automobiles, it is of great importance to separate and extract lithium resources called "energy metals" from different brines (salt lake brine, seawater brine and underground brine) at low cost. In particular, compared with other technologies, the adsorption method has attracted increasing attention in the related fields due to its low environmental pressure, simple process, wide applicable range (applicable to brines with a magnesium-lithium ratio of 1 to 2000), and low cost. The prepared lithium adsorbent with high adsorption capacity, high selectivity and strong anti-interference performance is one of the key technologies of the lithium extraction technology by the adsorption method.
Among a plurality of lithium adsorbents, a lithium-rich manganese lithium ion sieve precursor Li with a spinel structure is adopted 1.6 Mn 1.6 O 4 Prepared lithium ion sieve MnO 2 ·0.5H 2 O has a theoretical adsorption capacity as high as 72.3mg/g and is of interest. Preparation of the lithium ion Sieve precursor Li in general 1.6 Mn 1.6 O 4 The method comprises the following steps: the mixture of manganese source and lithium source is converted into intermediate product LiMnO by hydrothermal or solid phase method reaction 2 Then adding the intermediate product LiMnO 2 Calcination in an oxidizing atmosphere to form Li 1.6 Mn 1.6 O 4 . Compared with the hydrothermal method, the solid phase method is concerned by the industry due to the advantages of low equipment requirement, relatively simple preparation process and the like. Besides, relevant researches show that the lithium ion sieve precursor Li is prepared by taking manganese sesquioxide as a reactant and adopting a low-valence manganese oxide through a solid-phase reaction 1.6 Mn 1.6 O 4 Has more excellent adsorption performance. Manganese sesquioxide is usually prepared by roasting manganese carbonate, so that the properties of manganese carbonate, such as morphology, purity, dispersibility and the like, are influenced to different degrees, and further the properties of the manganese sesquioxide are influenced 1.6 Mn 1.6 O 4 The relative application performance of (2). Further, studies have shown that: micro-nano sized spinel type Li 1.6 Mn 1.6 O 4 The powder has the advantages of micron powder and nanometer powder, so the powder has application potential in industrial application.
Therefore, how to prepare Li having a low impurity content and a micro-nano size 1.6 Mn 1.6 O 4 Powder is a problem which is always sought to be solved in the industry.
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention provides a spinel type Li 1.6 Mn 1.6 O 4 The method for preparing the microsphere powder can prepare the Li with low impurity content and micron-nanometer size 1.6 Mn 1.6 O 4 Spherical powder.
In order to achieve the purpose, the invention adopts the following technical scheme:
spinel type Li 1.6 Mn 1.6 O 4 The preparation method of the microsphere powder comprises the following steps:
preparing soluble aluminum salt and soluble manganese salt to form a mixed salt solution, wherein the molar ratio of aluminum to manganese in the mixed salt solution is not more than 1: 6;
preparing a precipitant solution containing carbonate ions, and adding the precipitant solution into the mixed salt solution for precipitation reaction;
carrying out solid-liquid separation on the reaction liquid after the precipitation reaction is finished, and washing and drying the solid-phase product to obtain a first powder product containing manganese carbonate;
roasting the first powder product to obtain a second powder product containing manganese oxide;
mixing the second powder product with lithium salt powder to form mixed powder, sequentially carrying out first-stage roasting and second-stage roasting on the mixed powder, and cooling to obtain the spinel Li 1.6 Mn 1.6 O 4 Microsphere powder;
wherein the first stage roasting is carried out in an inert gas atmosphere, the second stage roasting is carried out in an oxygen atmosphere, and the roasting temperature of the first stage roasting is higher than that of the second stage roasting.
Preferably, the roasting temperature of the first section of roasting is 500-625 ℃, and the roasting time is 6-10 h; the roasting temperature of the second section of roasting is 400-500 ℃, and the roasting time is 4-8 h.
Preferably, the roasting temperature of the first stage roasting is 575-600 ℃, and the roasting temperature of the second stage roasting is 400-450 ℃.
Preferably, the first powder product is roasted for 0.5 to 3 hours at the temperature of 500 to 600 ℃ to obtain a second powder product containing manganese oxide.
Preferably, the soluble aluminium salt is selected from AlCl 3 、Al(NO 3 ) 3 、Al 2 (SO 4 ) 3 、Al 2 (SiO 3 ) 3 And Al 2 S 3 One or more than two of them.
Preferably, the soluble manganese salt is selected from MnCl 2 、MnSO 4 、Mn(CH 3 COO) 2 And Mn (NO) 3 ) 2 One or more than two of them.
Preferably, in the mixed salt solution, the molar ratio of aluminum to manganese is preferably 1 (6-9).
Preferably, the precipitant solution is selected from Na 2 CO 3 Solution, (NH) 4 ) 2 CO 3 Solution, NH 4 HCO 3 Solutions and K 2 CO 3 One or more than two of the solutions.
Preferably, the lithium salt powder is one or more of anhydrous lithium hydroxide, lithium carbonate, lithium chloride and lithium hydroxide monohydrate.
Preferably, the second powder product and the lithium salt powder are mixed according to a molar ratio of 1 (1-1.1) to form a mixed powder.
The embodiment of the invention provides spinel Li 1.6 Mn 1.6 O 4 The preparation method of the microsphere powder comprises the steps of adding soluble aluminum salt into raw materials for aluminum doping, and eliminating Li by adopting a lattice doping way 1.6 Mn 1.6 O 4 Impurity phase of (1), and preparation processThe roasting process with different process conditions is combined in a plurality of sections, so that the target product Li with high purity and micro-nano size is prepared 1.6 Mn 1.6 O 4 And (3) microsphere powder.
Drawings
FIG. 1 shows spinel type Li in examples of the present invention 1.6 Mn 1.6 O 4 A process flow diagram of a preparation method of microsphere powder;
FIG. 2 is Li prepared in example 1 of the present invention 1.6 Mn 1.6 O 4 XRD pattern of the powder;
FIG. 3 is Li prepared in example 1 of the present invention 1.6 Mn 1.6 O 4 FE-SEM image of the powder;
FIG. 4 shows Li prepared in example 2 of the present invention 1.6 Mn 1.6 O 4 XRD pattern of the powder;
FIG. 5 shows Li prepared in example 2 of the present invention 1.6 Mn 1.6 O 4 FE-SEM image of the powder;
FIG. 6 shows Li prepared in example 3 of the present invention 1.6 Mn 1.6 O 4 XRD pattern of the powder;
FIG. 7 shows Li prepared in example 3 of the present invention 1.6 Mn 1.6 O 4 FE-SEM image of the powder;
FIG. 8 shows Li obtained by preparation of example 4 of the present invention 1.6 Mn 1.6 O 4 XRD pattern of the powder;
FIG. 9 shows Li obtained by preparation of example 4 of the present invention 1.6 Mn 1.6 O 4 FE-SEM image of the powder;
FIG. 10 shows Li prepared in example 5 of the present invention 1.6 Mn 1.6 O 4 XRD pattern of the powder;
FIG. 11 shows Li prepared in example 5 of the present invention 1.6 Mn 1.6 O 4 FE-SEM image of the powder;
FIG. 12 shows Li prepared in example 6 of the present invention 1.6 Mn 1.6 O 4 XRD pattern of the powder;
FIG. 13 shows Li prepared in example 6 of the present invention 1.6 Mn 1.6 O 4 FE-SEM image of the powder;
FIG. 14 shows Li obtained by preparation of comparative example 1 1.6 Mn 1.6 O 4 XRD pattern of the powder;
FIG. 15 shows Li obtained by preparation of comparative example 1 1.6 Mn 1.6 O 4 FE-SEM image of the powder;
FIG. 16 shows Li obtained by the preparation of comparative example 2 1.6 Mn 1.6 O 4 XRD pattern of the powder;
FIG. 17 shows Li obtained in comparative example 2 1.6 Mn 1.6 O 4 FE-SEM image of the powder;
FIG. 18 shows Li obtained by the preparation of comparative example 3 1.6 Mn 1.6 O 4 XRD pattern of the powder;
FIG. 19 shows Li obtained in comparative example 3 1.6 Mn 1.6 O 4 FE-SEM image of the powder;
FIG. 20 shows Li obtained by the preparation of comparative example 4 1.6 Mn 1.6 O 4 XRD pattern of the powder;
FIG. 21 shows Li obtained by preparation of comparative example 4 1.6 Mn 1.6 O 4 FE-SEM image of the powder;
FIG. 22 shows Li obtained by preparation of comparative example 5 1.6 Mn 1.6 O 4 XRD pattern of the powder;
FIG. 23 shows Li obtained by preparation of comparative example 5 1.6 Mn 1.6 O 4 FE-SEM image of the powder;
FIG. 24 is Li obtained in comparative example 6 1.6 Mn 1.6 O 4 XRD pattern of the powder;
FIG. 25 shows Li obtained in comparative example 6 1.6 Mn 1.6 O 4 FE-SEM image of the powder;
FIG. 26 is Li obtained by preparation of comparative example 7 1.6 Mn 1.6 O 4 XRD pattern of the powder.
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 solution according to the present invention are shown in the drawings, and other details not so related to the present invention are omitted.
The embodiment of the invention provides spinel type Li 1.6 Mn 1.6 O 4 Referring to fig. 1, a method for preparing microsphere powder includes the following steps:
and S10, preparing soluble aluminum salt and soluble manganese salt to form a mixed salt solution, wherein the molar ratio of aluminum to manganese in the mixed salt solution is not more than 1: 6.
In particular, the soluble aluminium salt is selected from AlCl 3 、Al(NO 3 ) 3 、Al 2 (SO 4 ) 3 、Al 2 (SiO 3 ) 3 And Al 2 S 3 One or more than two of them. The soluble manganese salt is selected from MnCl 2 、MnSO 4 、Mn(CH 3 COO) 2 And Mn (NO) 3 ) 2 One or more than two of them.
In a preferable scheme, the molar ratio of aluminum to manganese in the mixed salt solution is preferably 1 (6-9).
And S20, preparing a precipitant solution containing carbonate ions, and adding the precipitant solution into the mixed salt solution to perform precipitation reaction.
Specifically, the precipitant solution is selected from Na 2 CO 3 Solution, (NH) 4 ) 2 CO 3 Solution, NH 4 HCO 3 Solutions and K 2 CO 3 One or more than two of the solutions. The concentration of the precipitant solution is preferably 0.55M.
Among them, the precipitation reaction is preferably carried out at room temperature with continuous stirring.
And step S30, carrying out solid-liquid separation on the reaction liquid after the precipitation reaction is finished, and washing and drying the solid-phase product to obtain a first powder product containing manganese carbonate.
In a preferable scheme, the solid-phase powder obtained by the reaction is washed to be neutral by deionized water, then a centrifuge is used for removing moisture, and then the obtained solid-phase powder is dried in a drying oven at 80 ℃.
And step S40, roasting the first powder product to obtain a second powder product containing manganese oxide. Wherein the manganese oxide contains Mn 2 O 3 、MnO 2 And Mn 3 O 4 。
In the preferred scheme, the first powder product is roasted for 0.5 to 3 hours at the temperature of 500 to 600 ℃.
Step S50, mixing the second powder product with lithium salt powder to form mixed powder, sequentially carrying out first-stage roasting and second-stage roasting on the mixed powder, and cooling to obtain the spinel type Li 1.6 Mn 1.6 O 4 Microsphere powder; wherein the first stage roasting is carried out in an inert gas atmosphere, the second stage roasting is carried out in an oxygen atmosphere, and the roasting temperature of the first stage roasting is higher than that of the second stage roasting.
The lithium salt powder is one or more of anhydrous lithium hydroxide, lithium carbonate, lithium chloride and lithium hydroxide monohydrate. The inert gas atmosphere is, for example, an argon atmosphere or a nitrogen atmosphere, and the oxygen atmosphere is, for example, a pure oxygen atmosphere or an air atmosphere.
In a preferable scheme, the second powder product and the lithium salt powder are mixed according to a molar ratio of 1 (1-1.1) to form mixed powder.
In a preferred scheme, the roasting temperature of the first-stage roasting is 500-625 ℃, and the roasting time is 6-10 h; the roasting temperature of the second stage of roasting is 400-500 ℃, and the roasting time is 4-8 h.
In a more preferable scheme, the roasting temperature of the first-stage roasting is 575-600 ℃, and the roasting temperature of the second-stage roasting is 400-450 ℃.
Spinel-type Li as described above 1.6 Mn 1.6 O 4 The preparation method of microsphere powder is characterized by that in the raw material a soluble aluminium salt is added to make aluminium doping, and the lattice doping approach is adopted to eliminate Li 1.6 Mn 1.6 O 4 The impurity phase in the Li-Li 1.6 Mn 1.6 O 4 And (3) microsphere powder.
Example 1
(1) Firstly, preparing 400mL of a manganese solution with the concentration of 0.3M from industrial-grade manganese salt by using deionized water, and naming the solution as 1. In this example, no aluminum salt was added, that is, the aluminum-manganese molar ratio was 0.
(2) Na in an amount of 0.55M 2 CO 3 160mL of the solution was designated as precipitant solution 2.
(3) And the solution 2 is poured into the solution 1, and the mixture is stirred for 10min at room temperature to carry out precipitation reaction.
(4) And washing the powder obtained after the precipitation reaction with deionized water to be neutral, removing water by adopting a centrifugal machine, and drying the obtained powder in a drying box at the temperature of 80 ℃ to obtain a first powder product containing manganese carbonate.
(5) And roasting the obtained first powder product in a muffle furnace at the temperature of 550 ℃ for 2h to obtain a second powder product containing manganese oxide.
(6) Weighing 3g of the prepared second powder product, mixing the second powder product with anhydrous lithium hydroxide according to a molar ratio of 1:1.1 to form mixed powder, roasting the mixed powder for 8 hours at 575 ℃ in an argon atmosphere, then reducing the temperature to 400 ℃ at 10 ℃/min, then roasting for 6 hours at constant temperature at 400 ℃ in an oxygen atmosphere, naturally cooling to room temperature after roasting is finished, and collecting a sample to obtain a product sample 1.
The analysis and characterization of the composition, structure and morphology of the product sample 1 were performed by X-ray diffraction (XRD) and field emission-scanning electron microscopy (FE-SEM), respectively.
FIG. 2 is a XRD analysis chart of product sample 1Figure of the figure results, as shown in figure 2, product sample 1 exhibited characteristic diffraction peaks representing the (111), (311), (222), (400), (331), (511), (440) and (531) crystal planes at 2 θ ═ 18.8 °, 36.6 °, 38.3 °, 44.5 °, 48.7 °, 58.9 °, 64.7 ° and 68.1 °, respectively, in comparison with standard card (PDF cardno.:52-1841), demonstrating that the product sample produced was Li 1.6 Mn 1.6 O 4 . Comparing the standard spectrum (fig. 2 diffraction curve a) and finding that: product sample 1 showed appearance at 2 θ of 15.5 °, 20.9 ° and 65.6 ° respectively representing orthorhombic LiMnO 2 (010) crystal plane of standard card (PDF Cardno.:86-0351) and Li 2 MnO 3 Characteristic diffraction peaks of (020) and (-331) crystal planes of (standard card (PDF Cardno.:73-0152)), the appearance of which proves that the sample contains LiMnO 2 And Li 2 MnO 3 Impurities.
The FE-SEM image of the product sample 1 is shown in FIG. 3, and it can be seen from FIG. 3 that the prepared product sample 1 is a porous spherical sample, which is a microsphere having a particle size of about 1.5 μm and comprising short rods having a primary particle size of about 100nm to 400nm in length and about 100nm in width.
Example 2
This example differs from example 1 in that: soluble aluminum salt is also added in the step (1), and deionized water is used for preparing 400mL of mixed solution with the total concentration of metal ions of 0.3M from industrial aluminum salt and manganese salt, wherein the molar ratio of aluminum to manganese in the mixed solution is 1: 9; in the step (6), the obtained mixed powder is firstly roasted for 8h at 625 ℃ in an argon atmosphere, then is reduced to 450 ℃ at a speed of 10 ℃/min, and then is roasted for 6h at a constant temperature of 450 ℃ in an oxygen atmosphere.
The rest of the process of this embodiment is the same as that of embodiment 1, and thus, the description thereof is omitted. The product obtained from this example preparation is designated product sample 2.
And respectively adopting an X-ray diffraction method and a field emission-scanning electron microscope method to analyze and characterize the components, the structure and the appearance of the product sample 2.
FIG. 4 is a diagram of Li prepared when the molar ratio of aluminum to manganese is 1:9 and the carbonizing precipitant is sodium carbonate 1.6 Mn 1.6 O 4 XRD Analyzer of powder sample 2And (5) characterizing a result graph. As shown in fig. 4, comparing with the standard card, sample 2 exhibited characteristic diffraction peaks representing the (111), (311), (222), (400), (331), (511), (440) and (531) crystal planes at 2 θ ═ 18.8 °, 36.6 °, 38.3 °, 44.5 °, 48.7 °, 58.9 °, 64.7 ° and 68.1 °, respectively, confirming that product sample 2 produced was Li, which is a product of Li 1.6 Mn 1.6 O 4 . No other diffraction peaks appeared in the diffractogram, demonstrating the high purity of the product sample 2 produced.
FIG. 5 shows Li being produced 1.6 Mn 1.6 O 4 FE-SEM image of product sample 2. As shown in FIG. 5, Li obtained in the present example 1.6 Mn 1.6 O 4 The product sample 2 was a porous, spherical powder having a particle size of about 1.5 μm composed of primary particles of about 50 nm.
Compared with the product sample 1 obtained in example 1, the product sample 2 of this example is doped with aluminum element, so that the prepared sample is pure Li 1.6 Mn 1.6 O 4 Phase, no other impurities. In addition, due to the doping of aluminum element, the prepared Li 1.6 Mn 1.6 O 4 Although the outer diameter size of the microsphere is not obviously changed, the primary particles of the microsphere are changed into spherical particles of about 50nm from short rods of 100 nm-400 nm and width of about 100nm, and the microsphere has a better appearance.
Example 3
This example differs from example 2 in that: adopting GaNO in the step (1) 3 ·3H 2 O replaces aluminum salt, and the molar ratio of gallium to manganese in the mixed solution is 1: 9.
The rest of the process in this embodiment is the same as that in embodiment 2, and thus, the description thereof is omitted. The product obtained from this example was designated product sample 3.
And respectively adopting an X-ray diffraction method and a field emission-scanning electron microscope method to analyze and characterize the components, the structure and the appearance of the product sample 3.
FIG. 6 is a diagram of Li prepared when the molar ratio of gallium to manganese is 1:9 and the carbonizing precipitant is sodium carbonate 1.6 Mn 1.6 O 4 XRD analysis characterization result chart of powder sample 3. As shown in FIG. 3, product samplesCharacteristic diffraction peaks at 2 θ of 18.8 °, 36.6 °, 38.3 °, 44.5 °, 48.7 °, 58.9 °, 64.7 °, 68.1 ° and 76.7 ° of 3, which proves that the main component of the produced product sample 3 is Li 1.6 Mn 1.6 O 4 . However, this sample showed the appearance of orthorhombic LiMnO at 2 θ of 15.5 °, 20.9 °, 33.1 ° and 65.6 °, respectively 2 (010) crystal face of (A) and orthorhombic LiMnO of tetragonal system 2 (103) crystal plane of (1) and Li 2 MnO 3 (Standard card (PDF Cardno.:73-0152, 2 theta ═ 20.9 degrees, 65.6 degrees)) and (-331) crystal plane characteristic diffraction peaks, the appearance of these peaks evidences that the sample contains LiMnO of different crystal systems 2 And Li 2 MnO 3 And the impurities are mixed, so that the doping of the gallium element instead of the aluminum element introduces more impurity phases, and the purity of the sample is not improved.
FIG. 7 is an FE-SEM image of product sample 3. As shown in FIG. 7, Li prepared after gallium doping 1.6 Mn 1.6 O 4 The powder sample is a porous, spherical powder having a particle diameter of about 1.2 μm formed of caterpillar-like primary particles, and the surface of the sample is relatively dense although some pores are present.
Example 4
The present example differs from example 1 in that: in the step (1), soluble aluminum salt is also added, and deionized water is used for preparing 400mL of mixed solution with the total metal ion concentration of 0.3M from industrial aluminum salt and manganese salt, wherein the molar ratio of aluminum to manganese in the mixed solution is 1: 6.
The rest of the process of this embodiment is the same as that of embodiment 1, and thus, the description thereof is omitted. The product obtained from this example preparation is designated product sample 4.
And respectively adopting an X-ray diffraction method and a field emission-scanning electron microscope method to analyze and characterize the composition, the structure and the appearance of the product sample 4.
FIG. 8 shows Li prepared when the molar ratio of Al to Mn is 1:6 and the carbonizing precipitant is sodium carbonate 1.6 Mn 1.6 O 4 XRD analysis characterization result chart of powder product sample 4. As shown in fig. 8, product sample 4 compared to the standard card at 2 θ ═ 18.8 °, 36.6 °, 38.3 °, 44.5 ° respectivelyCharacteristic diffraction peaks representing the crystal planes of (111), (311), (222), (400), (331), (511), (440) and (531) appearing at 48.7 °, 58.9 °, 64.7 ° and 68.1 °, demonstrating that the product sample 4 prepared is Li 1.6 Mn 1.6 O 4 . In addition, the diffraction pattern b of fig. 8 represents orthorhombic LiMnO at 2 θ of 15.4 ° 2 Characteristic diffraction peaks of (010) crystal plane and representative of Li at 2 θ of 20.9 ° and 65.6 ° 2 MnO 3 The characteristic diffraction peaks of the (020) and (-331) crystal planes of (A) are very weak, indicating that the sample has a very small amount of LiMnO 2 And Li 2 MnO 3 The impurity, however, showed a small amount of impurities because of its very weak peak intensity of characteristic diffraction.
FIG. 9 is an FE-SEM image of product sample 4. The increase in the amount of aluminum doping for the retention of Li, compared to example 2 1.6 Mn 1.6 O 4 The spherical powder particles are complete and have the assistance effect. As shown in FIG. 8, this product sample 4 was a porous, spherical powder having a particle size of about 1.5 μm and composed of primary short rod-shaped particles of about 100 to 200 nm.
Example 5
This example differs from example 4 in that: the molar ratio of aluminum to manganese in the step (1) is 1: 9; the precipitator solution prepared in the step (2) is (NH) 4 ) 2 CO 3 And (3) solution.
The rest of the process in this embodiment is the same as that in embodiment 4, and thus, the description thereof is omitted. The product obtained from this example was designated product sample 5.
And respectively adopting an X-ray diffraction method and a field emission-scanning electron microscope method to analyze and characterize the components, the structure and the appearance of the product sample 5.
FIG. 10 is a graph of Li prepared when the molar ratio of aluminum to manganese is 1:9 and the carbonizing precipitant is ammonium carbonate 1.6 Mn 1.6 O 4 XRD analysis characterization result chart of powder product sample 5. As shown in fig. 5, product sample 5 demonstrated the characteristic diffraction peaks representing the (111), (311), (222), (400), (331), (511), (440) and (531) crystal planes appearing at 2 θ ═ 18.8 °, 36.6 °, 38.3 °, 44.5 °, 48.7 °, 58.9 °, 64.7 ° and 68.1 °, respectively, as compared to the standard card, demonstrating that the prepared crystal planes wereProduct sample 5 is Li 1.6 Mn 1.6 O 4 . No other diffraction peaks appear in the diffraction pattern, which proves that the prepared sample has high purity.
FIG. 11 is an FE-SEM photograph of a product sample 5, as shown in FIG. 11, sample Li prepared in this example 1.6 Mn 1.6 O 4 Is a spherical powder having a particle size of about 1.5 μm and composed of primary particles of about 200 nm. When doping is performed at the same aluminum doping ratio as compared with sample 2 of example 2, both ammonium carbonate and sodium carbonate can be used as precipitants to prepare spherical Li 1.6 Mn 1.6 O 4 The only difference of the micron powder is that the sample 5 prepared by using ammonium carbonate as a precipitator has fewer surface holes and is relatively dense.
Example 6
This example differs from example 5 in that: the precipitator solution prepared in the step (2) is NH 4 HCO 3 And (3) solution.
The rest of the process in this embodiment is the same as that in embodiment 5, and thus, the description thereof is omitted. The product obtained from this example preparation is designated product sample 6.
And respectively adopting an X-ray diffraction method and a field emission-scanning electron microscope method to analyze and characterize the components, the structure and the appearance of the product sample 5.
FIG. 12 is a plot of Li prepared with a 1:9 molar ratio of aluminum to manganese and ammonium bicarbonate as the carbonation precipitant 1.6 Mn 1.6 O 4 XRD analysis characterization result chart of powder product sample 6. The characteristic diffraction peaks shown in FIG. 12 confirm that the product sample 6 prepared is Li 1.6 Mn 1.6 O 4 . And the purity of the sample is higher. FIG. 13 is an FE-SEM image of product sample 6, as shown in FIG. 13, of Li prepared 1.6 Mn 1.6 O 4 The agglomeration is serious in the powder, and the prepared powder is spherical particles with the particle size of about 500 nm.
Comparative example 1
Comparative example 1 is different from example 1 in that: the precipitator solution prepared in the step (2) is (NH) 4 ) 2 CO 3 And (3) solution. The rest of the process of comparative example 1 is the same as that of example 1, sinceThis will not be described in detail. The product obtained from the preparation of comparative example 1 is designated comparative product 1.
Comparative example 1 is intended to illustrate the effect of the carbonising precipitant and aluminium doping in the examples on the crystalline structure and morphology of the resulting product by comparison with examples 1 and 5.
And respectively adopting an X-ray diffraction method and a field emission-scanning electron microscope method to analyze and characterize the composition, the structure and the appearance of the comparative product 1.
Fig. 14 is a diagram showing the results of characterization by XRD analysis of comparative product 1, and as shown in fig. 14, in comparison with the standard card, comparative product 1 shows characteristic diffraction peaks representing (111), (311), (222), (400), (331), (511), (440) and (531) crystal planes at 2 θ ═ 18.8 °, 36.6 °, 38.3 °, 44.5 °, 48.7 °, 58.9 °, 64.7 ° and 68.1 °, respectively, demonstrating that comparative product 1 produced is Li 1.6 Mn 1.6 O 4 . No other diffraction peaks appear in the diffraction pattern, which proves that the prepared sample has high purity.
FIG. 15 is an FE-SEM photograph of comparative product 1, as shown in FIG. 15, although the product purity is high, Li was produced 1.6 Mn 1.6 O 4 The powder has no micron spherical size characteristics. In addition, as can be seen from comparison of FIGS. 11 and 15, although sample 5 of example 5 and comparative product 1 both prepared Li with higher purity using ammonium carbonate as a precipitant 1.6 Mn 1.6 O 4 The powder is quite different in morphology, and the aluminum doping is helpful for preparing Li with spherical micro-nano size 1.6 Mn 1.6 O 4 And (4) obtaining a target product.
Comparative example 2
Comparative example 2 differs from example 1 in that: the precipitator solution prepared in the step (2) is NH 4 HCO 3 And (3) solution. The remaining process of comparative example 2 is the same as that of example 1, and thus, will not be described again. Comparative example 2 the product obtained from the preparation is designated comparative product 2.
Comparative example 2 is intended to illustrate the effect of the carbonising precipitant and aluminium doping in the examples on the crystalline structure and morphology of the product obtained by comparison with examples 1 and 6.
And respectively adopting an X-ray diffraction method and a field emission-scanning electron microscope method to analyze and characterize the composition, the structure and the appearance of the comparison product 2.
Fig. 16 is a diagram showing the results of XRD analysis characterization of comparative product 2, and as shown in fig. 16, in comparison with the standard card, comparative product 2 shows characteristic diffraction peaks representing (111), (311), (222), (400), (331), (511), (440) and (531) crystal planes at 2 θ ═ 18.8 °, 36.6 °, 38.3 °, 44.5 °, 48.7 °, 58.9 °, 64.7 ° and 68.1 °, respectively, demonstrating that comparative product 2 produced is Li 1.6 Mn 1.6 O 4 . The diffraction pattern has a very weak representative of Li except at 20.9 ° 2 θ 2 MnO 3 (020) No other impurity peak appears except the characteristic diffraction peak of the crystal face, which proves that the prepared sample has higher purity.
FIG. 17 is an FE-SEM photograph of comparative product 2, and as shown in FIG. 17, Li was produced although the product purity was high 1.6 Mn 1.6 O 4 The powder has no micron spherical size characteristic, and the particle size of the powder is about 80 nm to 200 nm. In addition, as can be seen from fig. 12 corresponding to sample 6 of example 6, the aluminum doping can effectively promote the powder particle growth without introducing other impurity phases.
Comparative example 3
Comparative example 3 differs from example 1 in that: the precipitator solution prepared in the step (2) is Li 2 CO 3 And (3) solution. The remaining process of comparative example 3 is the same as that of example 1, and thus, will not be described again. Comparative example 3 the product obtained by the preparation is designated comparative product 3.
Comparative example 3 is intended to illustrate, by comparison with example 1, the effect of the carbonising precipitant in the examples on the crystalline structure and morphology of the resulting product.
And respectively adopting an X-ray diffraction method and a field emission-scanning electron microscope method to analyze and characterize the composition, the structure and the appearance of the comparison product 3.
Fig. 18 is a graph showing the results of XRD analysis characterization of comparative product 3, and as shown in fig. 18, a sample prepared using lithium carbonate as a precipitant contains many impurities. Fig. 19 is an FE-SEM image of comparative product 3, as shown in fig. 19, comparative product 3 having no microsphere size characteristics.
Comparative example 4
Comparative example 4 is different from example 1 in that: the prepared precipitator solution in the step (2) is K 2 CO 3 And (3) solution. The remaining process of comparative example 4 is the same as that of example 1, and thus, will not be described again. Comparative example 4 the product obtained from the preparation is designated comparative product 4.
Comparative example 4 is intended to illustrate, by comparison with example 1, the effect of the carbonising precipitant in the examples on the crystalline structure and morphology of the resulting product.
And respectively adopting an X-ray diffraction method and a field emission-scanning electron microscope method to analyze and characterize the composition, the structure and the appearance of the comparison product 4.
Fig. 20 is a diagram showing the results of characterization by XRD analysis of comparative product 4, and as shown in fig. 20, comparative product 4 shows characteristic diffraction peaks representing the (111), (311), (222), (400), (331), (511), (440) and (531) crystal planes at 2 θ ═ 18.8 °, 36.6 °, 38.3 °, 44.5 °, 48.7 °, 58.9 °, 64.7 ° and 68.1 °, respectively, demonstrating that comparative product 4 produced is Li 1.6 Mn 1.6 O 4 . In the diffractogram there is a very weak representative Li except at 20.9 ° 2 θ 2 MnO 3 (020) No other impurity peak appears except the characteristic diffraction peak of the crystal face, which proves that the prepared sample has higher purity.
FIG. 21 is an FE-SEM photograph of comparative product 4, which is shown in FIG. 21 as a uniformly dispersed Li sample prepared using potassium carbonate as a precipitant 1.6 Mn 1.6 O 4 The sample is nano-particles with the size of about 50nm and has no micron-size characteristics.
The following conclusions can be drawn by combining example 1 and comparative examples 1 to 4: lithium manganate Li prepared by lithium carbonate as precipitator 1.6 Mn 1.6 O 4 The impurity content in the sample is high, and the obtained powder has no micron size characteristic. Sodium carbonate, potassium carbonate, ammonium carbonate and ammonium bicarbonate as precipitating agents can successfully prepare target products Li with higher purity under the same conditions 1.6 Mn 1.6 O 4 But only sodium carbonate asThe precipitant can prepare Li with micron-nanometer size characteristics 1.6 Mn 1.6 O 4 The microspheres of the sample have a sphere diameter of about 1.5 μm. Under the same reaction condition, Li prepared by ammonium carbonate, ammonium bicarbonate and potassium carbonate without doping modification 1.6 Mn 1.6 O 4 The samples do not have micron and nanometer size characteristics
Comparative example 5
Comparative example 5 differs from example 1 in that: the calcination temperature in an argon atmosphere in step (6) was 625 ℃. The remaining process of comparative example 5 is the same as that of example 1, and thus, will not be described in detail. The product obtained by the preparation of comparative example 5 was designated comparative product 5.
Comparative example 5 is intended to illustrate the effect of the solid phase reaction argon atmosphere firing temperature and aluminum doping on the crystalline structure and morphology of the resulting product by comparison with examples 1 and 2.
And respectively adopting an X-ray diffraction method and a field emission-scanning electron microscope method to analyze and characterize the composition, the structure and the morphology of the comparison product 5.
FIG. 22 is a XRD analysis characterization result chart of comparative product 5, in which, as shown in FIG. 22, diffraction peaks of other impurities appear in the diffraction pattern, indicating that Li was prepared 1.6 Mn 1.6 O 4 The sample contained impurities. Fig. 23 is an FE-SEM image of the comparative product 5, and as shown in fig. 23, when the calcination temperature is 625 ℃ in an argon atmosphere, the micron-sized spherical morphology disappears, and thus the late solid-phase reaction conditions have a large influence on the purity and morphology of the target product. And example 2, when the calcination temperature is 625 ℃ in the argon atmosphere and aluminum doping is performed, it is also possible to prepare Li having a spherical micro-nano size 1.6 Mn 1.6 O 4 And (4) obtaining a target product.
Comparative example 6
Comparative example 6 differs from example 1 in that: the temperature of the calcination in an oxygen atmosphere in the step (6) was 450 ℃. The remaining process of comparative example 6 is the same as that of example 1, and thus, will not be described again. Comparative example 6 the product obtained by the preparation is designated comparative product 6.
Comparative example 6 is intended to illustrate the effect of oxygen atmosphere calcination temperature for solid phase reaction and aluminum doping on the crystal structure and morphology of the resulting product by comparison with examples 1 and 2.
And respectively adopting an X-ray diffraction method and a field emission-scanning electron microscope method to analyze and characterize the composition, the structure and the appearance of the comparison product 6.
Fig. 24 is a graph showing the results of XRD analysis characterization of comparative product 6, and as shown in fig. 24, the diffractogram of comparative product 6 has a very weak representative Li except at 20.9 ° 2 θ ═ 20.9 ° 2 MnO 3 (020) No other impurity peak appears except the characteristic diffraction peak of the crystal face, which proves that the prepared sample has higher purity. FIG. 25 is an FE-SEM photograph of comparative product 6, which is a solid powder sample of about 10 μm in irregular shape, showing that the micron-sized spherical morphology disappears as shown in FIG. 25 when the calcination temperature is 450 ℃ in an oxygen atmosphere. And example 2, when the firing temperature is 450 ℃ in the oxygen atmosphere and aluminum doping is performed, it is also possible to prepare Li having a spherical micro-nano size 1.6 Mn 1.6 O 4 And (4) obtaining a target product.
The results of the analyses of the product sample 1 of comparative example 1 and the product sample 2 of example 2 and of the comparative products 5 and 6 therefore show: the late solid phase reaction condition and aluminum doping have great influence on the purity and the appearance of the target product.
Comparative example 7
Comparative example 7 is different from example 1 in that: in the step (6), the molar ratio of the second powder product to the anhydrous lithium hydroxide is 1: 1.2. The remaining process of comparative example 7 is the same as that of example 1, and thus, will not be described in detail. Comparative example 7 the product obtained from the preparation is designated comparative product 7.
Comparative example 7 is intended to illustrate the effect of the molar ratio of lithium and manganese in the solid phase reaction on the resulting product by comparison with example 1.
Fig. 26 is a graph showing the results of XRD analysis characterization of comparative product 7, and as shown in fig. 26, comparative product 7 is characterized by 2 θ ═ 18.8 °, 36.6 °, 38.3 °, 44.5 °, 48.7 °, 58.9 °, 64.7 ° and 6.7 °, respectivelyThe characteristic diffraction peaks appearing at 8.1 ℃ and representing the (111), (311), (222), (400), (331), (511), (440) and (531) crystal planes, prove that comparative product 4 prepared is Li 1.6 Mn 1.6 O 4 . In addition, however, as indicated by the x-signs in the figures, impurity diffraction peaks also appeared at other angles, indicating that the sample was not pure.
In conclusion, the invention adds soluble aluminum salt into the raw material for aluminum doping, and eliminates Li by adopting a lattice doping way 1.6 Mn 1.6 O 4 The impurity phase in the raw material is mixed, and a roasting process with multiple sections of different process conditions is combined in the preparation process, so that the target product Li with high purity and micro-nano size is prepared 1.6 Mn 1.6 O 4 And (3) microsphere powder.
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 (7)
1. Spinel type Li 1.6 Mn 1.6 O 4 Preparation method of microsphere powder, spinel-type Li 1.6 Mn 1.6 O 4 The microsphere powder is used as a lithium ion sieve precursor for absorbing and extracting lithium, and is characterized in that the preparation method comprises the following steps:
preparing soluble aluminum salt and soluble manganese salt to form a mixed salt solution, wherein the molar ratio of aluminum to manganese in the mixed salt solution is 1 (6-9);
preparing a precipitant solution containing carbonate ions, and adding the precipitant solution into the mixed salt solution to perform a precipitation reaction;
carrying out solid-liquid separation on the reaction liquid after the precipitation reaction is finished, and washing and drying a solid-phase product to obtain a first powder product containing manganese carbonate;
roasting the first powder product to obtain a second powder product containing manganese oxide;
mixing the second powderMixing the product with lithium salt powder to form mixed powder, sequentially carrying out first stage roasting and second stage roasting on the mixed powder, and cooling to obtain the spinel type Li 1.6 Mn 1.6 O 4 Microsphere powder;
wherein the first stage roasting is carried out in an inert gas atmosphere, the roasting temperature is 575-600 ℃, and the roasting time is 6-10 h; the second-stage roasting is carried out in an oxygen atmosphere, the roasting temperature is 400-450 ℃, and the roasting time is 4-8 hours.
2. Spinel-type Li according to claim 1 1.6 Mn 1.6 O 4 The preparation method of the microsphere powder is characterized in that the first powder product is roasted for 0.5-3 h at the temperature of 500-600 ℃ to obtain a second powder product containing manganese oxide.
3. Spinel-type Li of claim 1 1.6 Mn 1.6 O 4 The preparation method of the microsphere powder is characterized in that the soluble aluminum salt is selected from AlCl 3 、Al(NO 3 ) 3 And Al 2 (SO 4 ) 3 One or more than two of them.
4. Spinel-type Li according to claim 1 1.6 Mn 1.6 O 4 The preparation method of the microsphere powder is characterized in that the soluble manganese salt is selected from MnCl 2 、MnSO 4 、Mn(CH 3 COO) 2 And Mn (NO) 3 ) 2 One or more than two of them.
5. Spinel-type Li according to claim 1 1.6 Mn 1.6 O 4 The preparation method of the microsphere powder is characterized in that the precipitant solution is selected from Na 2 CO 3 Solution, (NH) 4 ) 2 CO 3 Solution, NH 4 HCO 3 Solutions and K 2 CO 3 One or more than two of the solutions.
6. Spinel-type Li of claim 1 1.6 Mn 1.6 O 4 The preparation method of the microsphere powder is characterized in that the lithium salt powder is one or more than two of anhydrous lithium hydroxide, lithium carbonate, lithium chloride and lithium hydroxide monohydrate.
7. Spinel-type Li according to claim 6 1.6 Mn 1.6 O 4 The preparation method of the microsphere powder is characterized in that the second powder product and lithium salt powder are mixed according to the molar ratio of 1 (1-1.1) to form mixed powder.
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