CN103204545B - Prepare Emission in Cubic Li 4mn 5o 12method - Google Patents
Prepare Emission in Cubic Li 4mn 5o 12method Download PDFInfo
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- CN103204545B CN103204545B CN201310118834.8A CN201310118834A CN103204545B CN 103204545 B CN103204545 B CN 103204545B CN 201310118834 A CN201310118834 A CN 201310118834A CN 103204545 B CN103204545 B CN 103204545B
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- solid phase
- lithium
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Abstract
The present invention relates to one and prepare Emission in Cubic Li
4mn
5o
12method, the key step of described method is: in air atmosphere, is calcined at least 6 hours, obtain target compound by the solid-phase mixture formed primarily of solid phase manganous salt and solid phase lithium salts or/and solid phase hydrogen Lithium Oxide 98min in 350 DEG C ~ 500 DEG C; Wherein, the mol ratio of manganese element and elemental lithium is (0.6 ~ 2): 1.The present invention has 1. cheaper starting materials and is easy to get, and the mol ratio of elemental lithium and manganese element is lower, few containing lithium wastage of material; 2. preparation condition comparatively gentle (be embodied in calcining temperature not high and without the need to protection of inert gas), the advantage such as preparation process is simple, preparation cycle is short.Emission in Cubic Li prepared by the present invention
4mn
5o
12there is spinel structure, stable in properties, can be used as the electrode materials of lithium cell, or as preparing lithium ion sieve (MnO
20.31H
2o) presoma.
Description
Technical field
The present invention relates to a kind of preparation method of Emission in Cubic ternary compound oxides, specifically, relate to one and prepare Emission in Cubic Li
4mn
5o
12method.
Background technology
Emission in Cubic Li
4mn
5o
12, because it has large electrical capacity and good cyclical stability in 3V region, can be used as the electrode materials of lithium cell.In addition, Emission in Cubic Li
4mn
5o
12lithium ion sieve (MnO can be obtained after " de-lithium "
20.31H
2o), this lithium ion sieve (MnO
20.31H
2o) be particularly suitable for from containing enrichment extraction lithium lower concentration lithium high concentration impurities solution lithium-containing solutions such as (as:) salt lake brine, well water and seawater.
So far, Emission in Cubic Li is prepared
4mn
5o
12method mainly contain " sol-gel method " and " hydrothermal method ", they are each has something to recommend him.But no matter be " sol-gel method " or " hydrothermal method ", all there is the defect that operating process is complicated and preparation cycle is longer.
Given this, the Emission in Cubic Li that a kind of operating process is relatively simple and preparation cycle is shorter is provided
4mn
5o
12preparation method become the technical issues that need to address of the present invention.
Summary of the invention
One object of the present invention is, provides a kind of " solid phase method " to prepare Emission in Cubic Li
4mn
5o
12method, overcome the defect existed in prior art.
Of the present inventionly prepare Emission in Cubic Li
4mn
5o
12method, its key step is: in air atmosphere, primarily of solid phase manganous salt and solid phase lithium salts or/and the solid-phase mixture that solid phase hydrogen Lithium Oxide 98min forms is calcined at least 6 hours in 350 DEG C ~ 500 DEG C, obtains target compound (Emission in Cubic Li
4mn
5o
12); Wherein, the mol ratio of manganese element and elemental lithium is (0.6 ~ 2): 1.
Adopt Li prepared by aforesaid method
4mn
5o
12through X-ray diffraction analysis, its crystal formation can be determined; And by existing elemental analysis method, its molecular formula can be established.
In addition, a further object of the invention is, provides one to prepare lithium ion sieve (MnO
20.31H
2o) method, the key step of described method is: with Emission in Cubic Li
4mn
5o
12for presoma, after " de-lithium ", obtain target compound (lithium ion sieve: MnO
20.31H
2o), it is characterized in that, wherein said Emission in Cubic Li
4mn
5o
12the method following by key step obtains:
In air atmosphere, calcined at least 6 hours in 350 DEG C ~ 500 DEG C by the solid-phase mixture formed primarily of solid phase manganous salt and solid phase lithium salts or/and solid phase hydrogen Lithium Oxide 98min, obtain target compound (Emission in Cubic Li
4mn
5o
12); Wherein, the mol ratio of manganese, lithium is (0.6 ~ 2): 1.
From above-mentioned technological method, tool of the present invention has the following advantages:
1, cheaper starting materials is easy to get, and the mol ratio of elemental lithium and manganese element is lower, few containing lithium wastage of material;
2, preparation condition is comparatively gentle: be not embodied in calcining temperature high and without the need to protection of inert gas;
3, prepared Emission in Cubic Li
4mn
5o
12, it has spinel structure (known through X-ray diffraction analysis), and stable in properties can be used as the electrode materials of lithium cell, or as preparing lithium ion sieve (MnO
20.31H
2o) presoma.
Accompanying drawing explanation
Fig. 1. Emission in Cubic Li prepared by embodiment of serving as reasons 1 ~ 3
4mn
5o
12xRD figure,
Wherein, X-ray diffractometer is with the whole diffraction region of the angle scanning of 2 θ.
Fig. 2. Emission in Cubic Li prepared by embodiment of serving as reasons 1
4mn
5o
12sEM figure.
Fig. 3. ion(ic)sieve (MnO prepared by embodiment of serving as reasons 5
20.31H
2o) XRD figure,
Wherein, X-ray diffractometer is with the whole diffraction region of the angle scanning of 2 θ.
Fig. 4. ion(ic)sieve (MnO prepared by embodiment of serving as reasons 5
20.31H
2o) SEM figure.
Embodiment
In the present invention's preferred technical scheme, described solid phase manganous salt is selected from: the mixture of one or two or more kinds (containing two kinds) in the oxysalt of solid phase bivalent manganese or the halogenide of solid phase bivalent manganese;
Further optimal technical scheme is: described solid phase manganous salt is selected from: solid phase manganous carbonate (MnCO
3), solid phase manganous sulfate (MnSO
4), solid phase manganous fluoride (MnF
2), solid-phase chlorination manganese (MnCl
2) or solid phase manganese iodide (MnI
2) in the mixture of one or two or more kinds (containing two kinds).
In another preferred technical scheme of the present invention, described solid phase lithium salts is selected from: the mixture of one or two or more kinds (containing two kinds) in the oxysalt of solid phase lithium or the halogenide of solid phase lithium;
Further optimal technical scheme is: described solid phase lithium salts is selected from: solid phase lithium nitrate (LiNO
3), solid phase Quilonum Retard (Li
2cO
3) or solid-phase chlorination lithium (LiCl) in the mixture of one or two or more kinds (containing two kinds).
In a further preferred technical solution of the present invention, the solid-phase mixture be made up of solid phase manganous salt and solid phase lithium salts or/and solid phase hydrogen Lithium Oxide 98min is calcined 6 hours ~ 24 hours (preferred calcination time is 12 hours ~ 24 hours) in 350 DEG C ~ 450 DEG C.
In sum, provided by the inventionly Emission in Cubic Li is prepared
4mn
5o
12method, comprise the steps:
(1) by solid phase manganous salt and solid phase lithium salts or/and solid phase hydrogen Lithium Oxide 98min grinds and mixes, obtain solid-phase mixture, in described solid-phase mixture, the mol ratio of manganese element and elemental lithium is (0.6 ~ 2): 1;
(2) by gained solid-phase mixture in 350 DEG C ~ 450 DEG C and calcine 12 little of 24 hours in dynamic air atmosphere, obtain target compound (Emission in Cubic Li
4mn
5o
12).
In addition, by gained Emission in Cubic Li
4mn
5o
12lithium ion sieve (MnO is obtained again through " de-lithium (namely first after soaking de-agent leaching, drier) "
20.31H
2o), wherein said leaching takes off agent and can be: concentration is the hydrochloric acid of 0.1mol/L ~ 1mol/L, sulfuric acid, nitric acid, hypochlorous acid, chloric acid, perchloric acid or ammonium sulphite.
Below by embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
Embodiment 1
14.9g Manganous sulfate monohydrate and 3.7g mono-hydronium(ion) Lithium Oxide 98min are ground evenly in mortar; Transfer in retort furnace by the mixture obtained, calcine 24 hours under 350 DEG C of conditions, wherein air velocity is 50mL/min, obtains Emission in Cubic Li
4mn
5o
12, the XRD figure of this product is shown in Fig. 1, and SEM figure is shown in Fig. 2; From Fig. 1,2, the Li of pure phase can be obtained under adopted calcination condition
4mn
5o
12, and product particle size is more even.
Embodiment 2
By grinding in 4.6g manganous carbonate and 1.7g Quilonum Retard mortar evenly; Transfer in retort furnace by the mixture obtained, calcine 24 hours under 400 DEG C of conditions, wherein air velocity is 50mL/min, obtains Li
4mn
5o
12, the XRD figure of this product is shown in Fig. 1.
Embodiment 3
By grinding in 4.6g Manganous chloride tetrahydrate and 1.7g lithium chloride mortar evenly; Transfer in retort furnace by the mixture obtained, calcine 24 hours under 450 DEG C of conditions, wherein air velocity is 100mL/min, obtains Li
4mn
5o
12, the XRD figure of this product is shown in Fig. 1.
Embodiment 4
By the Emission in Cubic Li prepared by embodiment 1
4mn
5o
120.8g adds 200mL0.1mol/L (NH
4)
2s
2o
8solution, puts into water bath with thermostatic control vibrator with the hunting of frequency of 130rpm, and control temperature is constant in 30 DEG C, and the Li in presoma is deviate from reaction 12h leaching
+; Further filtration, to wash completely with deionized water, be less than 10 with the ratio conductance of washings
-5Ω
-1m
-1for standard, suction filtration, dry 3h in 60 DEG C of still airs, namely obtain ion(ic)sieve sorbent material MnO of the present invention
20.31H
2o.The molten damage of this acid cleaning process manganese is 1%.
Embodiment 5
By the Li prepared by embodiment 2
4mn
5o
120.8g adds 200mL0.1mol/L HCl solution, puts into water bath with thermostatic control vibrator with the hunting of frequency of 130rpm, and control temperature is constant in 30 DEG C, and the Li in presoma is deviate from reaction 12h leaching
+; Further filtration, to wash completely with deionized water, be less than 10 with the ratio conductance of washings
-5Ω
-1m
-1for standard, suction filtration, dry 8h in 120 DEG C of still airs, namely obtain ion(ic)sieve of the present invention.This ion(ic)sieve XRD figure is shown in Fig. 3, and this ion(ic)sieve SEM figure is shown in Fig. 4; Fig. 1 and Fig. 3 contrast can be found, before and after pickling, structure there is no obvious change, is still spinel structure.As shown in Figure 4, after pickling, ion(ic)sieve particle diameter slightly diminishes.
Embodiment 6
Take the sample (ion(ic)sieve) of 100mg prepared by embodiment 4 and put into tool plug Erlenmeyer flask, add 10mL10mmol/L mixed ion solutions (Li
+, Na
+, K
+, Ca
2+, and Mg
2+, pH=10.1), be placed in the large-scale shaking table of intelligent multifunctional with the hunting of frequency of 130rpm, control temperature is constant in 30 DEG C, reaction 120h, gets the concentration that supernatant liquid IC monitors wherein each ion, the results are shown in Table the adsorption selectivity of 1(ion(ic)sieve).
Table 1
In table 1, C
0refer to the concentration of absorption original solution intermediate ion; C
ethat absorption reaches the rear effects of ion concentration of balance; Q
eit is the adsorptive capacity that absorption reaches the rear ion of balance; CF is concentration factor; K
dand α
li methe partition ratio of coexisting ion and the selectivity coefficient of lithium ion respectively.
As shown in Table 1, compared with common coexisting ion, this ion(ic)sieve has higher selectivity to lithium, carries lithium and Extracting Lithium from Seawater has important practical value to salt lake.
Embodiment 7
Tool plug Erlenmeyer flask put into by the sample (ion(ic)sieve) taken prepared by 100mg embodiment 5, add in 100mL30mmol/LLiCl solution, with ammoniacal liquor-ammonium chloride buffer solution regulator solution pH=10.1, be placed in the large-scale shaking table of intelligent multifunctional with the hunting of frequency of 130rpm, control temperature is constant in 30 DEG C, reaction 48h, get the concentration that supernatant liquid IC monitors wherein lithium ion, the adsorptive capacity of ion(ic)sieve is 6mmol/g.
From the various embodiments described above, synthetic method of the present invention, experiment condition, product proportioning easily control, and the condition and range that can obtain desired product is wide; The present invention synthesizes the ion(ic)sieve sorbent material MnO obtained
20.31H
2o, it can be used for the lithium-containing solution such as salt lake brine, seawater and carries lithium, and it is large to have adsorptive capacity, reproducible advantage.
Claims (4)
1. prepare Emission in Cubic Li for one kind
4mn
5o
12method, it is characterized in that, the key step of described method is: in air atmosphere, primarily of solid phase manganous salt and solid phase lithium salts or/and the solid-phase mixture that solid phase hydrogen Lithium Oxide 98min forms calcines 6 hours ~ 24 hours in 350 DEG C ~ 450 DEG C, obtains target compound;
Wherein, described solid phase manganous salt is selected from: one or two or more kinds mixture in the oxysalt of solid phase bivalent manganese or the halogenide of solid phase bivalent manganese; Described solid phase lithium salts is selected from: one or two or more kinds mixture in the oxysalt of solid phase lithium or the halogenide of solid phase lithium; The mol ratio of manganese element and elemental lithium is (0.6 ~ 2): 1.
2. the method for claim 1, is characterized in that, wherein calcination time is 12 hours ~ 24 hours.
3. method as claimed in claim 1 or 2, it is characterized in that, solid phase manganous salt wherein used is selected from: one or two or more kinds mixture in solid phase manganous carbonate, solid phase manganous sulfate, solid phase manganous fluoride, solid-phase chlorination manganese or solid phase manganese iodide.
4. method as claimed in claim 1 or 2, it is characterized in that, solid phase lithium salts wherein used is selected from: one or two or more kinds mixture in solid phase lithium nitrate, solid phase Quilonum Retard or solid-phase chlorination lithium.
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| CN103991908B (en) * | 2014-05-08 | 2016-04-20 | 华东理工大学 | By the method for cation doping regulation and control lithium ion sieve stability |
| CN108199104A (en) * | 2017-11-30 | 2018-06-22 | 湖南邦普循环科技有限公司 | A kind of lithium manganate battery waste material prepares the method and its lithium ion sieve of lithium ion sieve |
| CN108579661B (en) * | 2018-05-09 | 2019-11-05 | 中南大学 | A kind of doped modified lithium ion sieve and preparation method thereof, application |
| CN117101599A (en) * | 2023-08-04 | 2023-11-24 | 香港中文大学（深圳） | Lithium ion sieve adsorbent material and preparation method and application thereof |
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Non-Patent Citations (1)
| Title |
|---|
| 低维纳米立方相Li4Mn5O12的制备及锂吸附性能;孙淑英等;《无机材料学报》;20100630;第25卷(第6期);第626-630页 * |
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