CN116371387A - Preparation method of cation doped modified lithium ion sieve - Google Patents
Preparation method of cation doped modified lithium ion sieve Download PDFInfo
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- CN116371387A CN116371387A CN202310175726.8A CN202310175726A CN116371387A CN 116371387 A CN116371387 A CN 116371387A CN 202310175726 A CN202310175726 A CN 202310175726A CN 116371387 A CN116371387 A CN 116371387A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical class [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 150000001768 cations Chemical class 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011572 manganese Substances 0.000 claims abstract description 95
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 29
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- 229910015645 LiMn Inorganic materials 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 150000002696 manganese Chemical class 0.000 claims description 13
- 230000000630 rising effect Effects 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 235000006748 manganese carbonate Nutrition 0.000 claims description 5
- 239000011656 manganese carbonate Substances 0.000 claims description 5
- 229940093474 manganese carbonate Drugs 0.000 claims description 5
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 5
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910013553 LiNO Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229940099594 manganese dioxide Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- QWYFOIJABGVEFP-UHFFFAOYSA-L manganese(ii) iodide Chemical compound [Mn+2].[I-].[I-] QWYFOIJABGVEFP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 21
- 238000004090 dissolution Methods 0.000 abstract description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052748 manganese Inorganic materials 0.000 abstract description 17
- 239000003463 adsorbent Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 3
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 25
- 239000000243 solution Substances 0.000 description 24
- 239000010949 copper Substances 0.000 description 14
- 239000011701 zinc Substances 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052596 spinel Inorganic materials 0.000 description 11
- 239000011029 spinel Substances 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 10
- 239000010431 corundum Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 230000020477 pH reduction Effects 0.000 description 10
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000012267 brine Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 5
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 229910014689 LiMnO Inorganic materials 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 2
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- VJFCXDHFYISGTE-UHFFFAOYSA-N O=[Co](=O)=O Chemical compound O=[Co](=O)=O VJFCXDHFYISGTE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- QEXMICRJPVUPSN-UHFFFAOYSA-N lithium manganese(2+) oxygen(2-) Chemical class [O-2].[Mn+2].[Li+] QEXMICRJPVUPSN-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3057—Use of a templating or imprinting material ; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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Abstract
The invention discloses a preparation method of a cation doping modified lithium ion sieve, wherein the molecular formula of the cation doping modified lithium ion sieve is Li 1.6 R x Mn 1.6‑x O 4 . According to the preparation method of the cation doped modified lithium ion sieve, the used raw materials are low in price, the synthesis method is simple, the waste of lithium salt raw materials is low, the lithium-manganese ratio is low, and the obtained product is high in purity and single in crystalline phase, so that industrialization is facilitated. Compared with the original adsorbent, the modified adsorbent has high adsorption capacity, and the manganese dissolution loss rate is reduced, so that the selectivity of the modified adsorbent to lithium ions is high.
Description
Technical Field
The invention belongs to the technical field of preparation of ion sieves, and particularly relates to a preparation method of a cation doped modified lithium ion sieve.
Background
Lithium and its derivatives in the form of ceramics or glass play a key role in a variety of commercial applications such as batteries, pharmaceuticals and lubricants, and have become strategic technology elements. As the demand for electronic devices and electric vehicles increases, the global demand for lithium resources increases dramatically. At presentThe main sources of lithium are brine deposits in south america (chile, bolivia and argentina), followed by hard rock resources, of which the continental brine resource is the largest, except for seawater. It is important to separate and extract lithium ions from these resources for ten minutes. The lithium ion sieve technology can realize high adsorption capacity, high lithium selectivity, environmental friendliness and high-purity lithium products, and from the perspective of a metal transition framework, the lithium ion sieve can be mainly obtained from two precursor materials, namely lithium manganese oxide and lithium titanium oxide. Compared with lithium titanium oxide, spinel type lithium manganese oxide has the advantages of large lithium adsorption capacity, good regeneration performance, simple synthesis and the like, and is the most widely applied precursor material. Wherein Li is 1.6 Mn 1.6 O 4 Has higher theoretical adsorption capacity and lower Mn loss rate, thus being a main adsorbent for recovering lithium in solution, and the micro doping can further improve the performance and the cycle stability. Chitrakar et al synthesized Li 4 Fe x Mn 5-x O 12 As a result, it was found that as the Fe/Mn ratio increased, the dissolution of Mn decreased, li + The adsorption amount of (a) increases. However, elemental doping is to Li 1.6 Mn 1.6 O 4 Adsorption of Li + Is rarely studied. The patent application publication No. CN103991908A discloses a method for regulating and controlling the stability of a lithium ion sieve by cation doping, and adopts a solid phase method to carry out solid phase Li 4 Mn 5 O 12 The composite oxide is doped with metal ions. Due to Li 1.6 Mn 1.6 O 4 Cannot be directly synthesized, and LiMnO is synthesized by hydrothermal reaction 2 Then LiMnO is added 2 Roasting in air at low temperature. The preparation of uniformly doped lithium manganese oxide by a one-step method is not reported in the literature.
Disclosure of Invention
The invention aims to provide a preparation method of a cation doped modified lithium ion sieve.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a method for preparing a cation doped modified lithium ion sieve, comprising the following steps:
the first step: ultrasonically dissolving target doped element salt in a solvent, fully dissolving, slowly pouring manganese salt into the solvent, continuously ultrasonically treating the solution for 1 to 5 hours, drying the solution for 1 to 12 hours at the temperature of between 50 and 80 ℃, and calcining the solution for 3 to 12 hours at the temperature of between 500 and 800 ℃ in an air atmosphere to obtain metal doped modified Mn 2-x R x O 3 ；
Or mixing the target doping element salt and manganese salt uniformly, calcining for 3-12 h at 500-800 ℃ in air atmosphere to obtain metal doping modified Mn 2-x R x O 3 ；
In the target doping element salt and the manganese salt, the mol ratio of R to Mn is (0.01-0.18): 1;
doping metal modified Mn 2-x R x O 3 Grinding and mixing lithium salt, mn 2-x R x O 3 And a lithium salt wherein the molar ratio of Li to Mn is (1-1.2): 1; fully reacting for 1-72 hours at the temperature of 100-180 ℃, and drying to obtain LiMn 1-x R x O 2 A powder;
the target doping element salt is selected from acetate, sulfate, nitrate or carbonate of at least one Ti, fe, co, cu, ni, zn, zr, ce of the following elements;
the manganese salt is at least one selected from manganese acetate, manganese carbonate, manganese sulfate, manganese dioxide and manganese iodide;
the lithium salt is selected from LiOH.H 2 O、LiNO 3 Or Li (lithium) 2 CO 3 At least one of (a) and (b);
and a second step of: liMn obtained in the first step 1-x R x O 2 Calcining the powder for 4-72 h at 300-500 ℃ in air atmosphere to obtain lithium ion sieve precursor Li 1.6 R x Mn 1.6-x O 4 A powder;
and a third step of: lithium ion sieve precursor Li prepared in the second step 1.6 R x Mn 1.6-x O 4 Washing the powder with acid, filtering, washing with deionized water, and drying to obtain the cation doped modified lithium ion sieve Li 1.6 R x Mn 1.6-x O 4 ；
The molecular formula of the cation doped modified lithium ion sieve is Li 1.6 R x Mn 1.6-x O 4 R is selected from at least one of the following: ti, fe, co, cu, ni, zn, zr, ce, x is more than or equal to 0.01 and less than or equal to 0.25.
The target doping element salt in the first step is selected from Ni (NO 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·6H 2 O、Zn(NO 3 ) 2 ·6H 2 O、FeCl 3 。
The solvent in the first step is selected from ethanol.
The temperature rising rate in the first step is 1-10 ℃/min, preferably 5 ℃/min.
The temperature rising rate in the second step is 1-10 ℃/min, preferably 5-10 ℃/min.
The acid in the third step is selected from hydrochloric acid, sulfuric acid or nitric acid.
The concentration of the acid in the third step is 0.1-0.5 mol/L, and the soaking time is 24-48h.
By adopting the technical scheme, the invention has the following advantages and beneficial effects:
according to the preparation method of the cation doped modified lithium ion sieve, the used raw materials are low in price, the synthesis method is simple, the waste of lithium salt raw materials is low, the lithium-manganese ratio is low, and the obtained product is high in purity and single in crystalline phase, so that industrialization is facilitated. Compared with the original adsorbent, the modified adsorbent has high adsorption capacity, and the manganese dissolution loss rate is reduced, so that the selectivity of the modified adsorbent to lithium ions is high.
The preparation method of the cation doped modified lithium ion sieve provided by the invention is to prepare different cation doped modified lithium manganese oxides by a hydrothermal method, so that the influence of cation doping on the adsorption quantity of lithium ions in salt lake brine is examined.
According to the preparation method of the cation doped modified lithium ion sieve, the uniformly doped lithium manganese oxide is synthesized through a one-step hydrothermal method in the doping process, so that the doping process is different from other doped ion sieves. The method has the advantages of simple process route, mild preparation conditions, short reaction period and higher adsorption performance and stability of the doped lithium manganese oxide.
Drawings
FIG. 1 is LiMn in example 1 1-x Fe x O 2 And Li (lithium) 1.6 Fe x Mn 1.6-x O 4 An XRD pattern of (C) is shown in the figure.
FIG. 2 shows LiMn in examples 2 to 5 1-x R x O 2 An XRD pattern of (C) is shown in the figure.
FIG. 3 is Li in examples 2 to 5 1.6 R x Mn 1.6-x O 4 An XRD pattern of (C) is shown in the figure.
FIG. 4 is a cation-doped modified lithium ion sieve Li of example 2 1.6 Ni x Mn 1.6-x O 4 Is intended for TEM illustration.
FIG. 5 is LiMn in example 3 1-x Co x O 2 Is a schematic of SEM image.
FIG. 6 is LiMn in example 4 1-x Cu x O 2 Is a schematic of a TEM profile of (a).
FIG. 7 is Li in examples 2 to 5 1.6 R x Mn 1.6-x O 4 Is intended to be an SEM illustration of (c).
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
The molecular formula of the cation doped modified lithium ion sieve provided by the invention is Li 1.6 R x Mn 1.6-x O 4 Wherein x is more than or equal to 0.01 and less than or equal to 0.25; the dissolution loss rate of manganese in the pickling process is further reduced through cation doping, and the adsorption quantity in salt lake brine can be improved. The synthesis method is simple, and the original doped ions can not be changed by introducingSpinel structures and other impurity ions.
Example 1
The preparation method of the cation doped modified lithium ion sieve comprises the following steps:
the first step: 15g of MnCO 3 And 3.15g FeCl 3 Calcining for 5 hours at 800 ℃ in an air atmosphere after uniformly mixing, wherein the temperature rising rate is 5 ℃/min during calcining to obtain the iron doped Mn 2-x Fe x O 3 The method comprises the steps of carrying out a first treatment on the surface of the In the target doping element salt and the manganese salt, the molar ratio of Fe to Mn is 0.15:1.
Will be 8.55g Mn 2-x Fe x O 3 And 5g of LiOH H 2 O is ground and mixed for 2 hours, and the molar ratio of Li to Mn is 1.1:1; fully reacting for 48 hours in a reaction kettle at the temperature of 120 ℃, and drying to obtain 11g of LiMn 1-x Fe x O 2 A powder;
and a second step of: 5g of LiMn obtained in the first step 1-x Fe x O 2 Placing the powder into a corundum crucible, placing the corundum crucible into a muffle furnace, calcining for 24 hours at 400 ℃ in an air atmosphere, wherein the temperature rising rate is 5 ℃/min during calcining, and then naturally cooling to obtain 5.4 g Li of the spinel type lithium ion sieve precursor modified by iron doping 1.6 Fe x Mn 1.6-x O 4 (x=0.24) powder.
And a third step of: 0.5g of lithium ion sieve precursor Li prepared in the second step 1.6 Fe x Mn 1.6-x O 4 The powder is soaked in 0.3mol/L HCl100mL for acidification treatment for 36h; and (3) carrying out suction filtration on the solution after the acidification treatment, washing the solution with deionized water for three times, and then drying the solution at 60 ℃ to obtain 0.5g of the cation doped modified lithium ion sieve.
The molecular formula of the cation doped modified lithium ion sieve is Li 1.6 Fe x Mn 1.6-x O 4 ，x＝0.24。
FIG. 1 is LiMn in example 1 1-x Fe x O 2 And Li (lithium) 1.6 Fe x Mn 1.6-x O 4 An XRD pattern of (C) is shown in the figure. As can be seen from the figure, the doping amount of iron is 15% and the doping amount of iron is equal to that of the orthorhombic phase LiMnO 2 、Li 1.6 Fe x Mn 1.6-x O 4 The standard patterns of the ion sieve are consistent, and the ion sieve has stronger peak intensity, which shows that the crystallinity of the ion sieve modified by iron doping is good.
Example 2
The preparation method of the cation doped modified lithium ion sieve comprises the following steps:
the first step: 2.53g of target doping element salt Ni (NO 3 ) 2 ·6H 2 O is dissolved in 10mL of ethanol by ultrasonic, and 20g of MnCO is slowly poured after the O is fully dissolved 3 Continuing to carry out ultrasonic treatment for 2 hours, drying for 12 hours at the temperature of 60 ℃, then calcining for 5 hours at 800 ℃ under the air atmosphere, wherein the temperature rising rate is 5 ℃/min during calcining, and 14g of metal doped modified Mn is obtained 2-x Ni x O 3 The method comprises the steps of carrying out a first treatment on the surface of the In the target doping element salt and the manganese salt, the mole ratio of Ni to Mn is 0.05:1.
8.55g of metal-doped modified Mn 2-x Ni x O 3 、5gLiOH·H 2 O is ground and mixed for 2 hours, mn 2-x Ni x O 3 And a molar ratio of Li to Mn in the lithium salt of 1.1:1; fully reacting for 48 hours in a reaction kettle at 130 ℃, centrifugally drying to obtain 11g of LiMn 1-x Ni x O 2 A powder;
and a second step of: 5g of LiMn obtained in the first step 1-x Ni x O 2 Placing the powder into a corundum crucible, placing the corundum crucible into a muffle furnace, calcining for 5 hours at 450 ℃ in an air atmosphere, wherein the temperature rising rate is 5 ℃/min during calcining, and then naturally cooling to obtain the spinel type lithium ion sieve precursor 5.3gLi 1.6 Ni x Mn 1.6-x O 4 (x=0.080) powder.
And a third step of: the lithium ion sieve precursor prepared in the second step is 0.1gLi 1.6 Ni 0.08 Mn 1.52 O 4 Soaking the powder in 200mL of sulfuric acid with the concentration of 0.5mol/L for acidification treatment for 24h, and eluting lithium ions in the precursor; and (3) carrying out suction filtration on the solution after the acidification treatment, washing the solution with deionized water for three times, and then drying the solution at 60 ℃ to obtain 0.5g of the cation doped modified lithium ion sieve.
The molecular formula of the cation doped modified lithium ion sieve is Li 1.6 Ni x Mn 1.6-x O 4 ，x＝0.08。
XRD spectra of the product are shown in figures 2 and 3, SEM spectra are shown in figure 7 a, and TEM spectra are shown in figure 4. FIG. 2 shows LiMn in examples 2 to 5 1-x R x O 2 An XRD pattern of (C) is shown in the figure. FIG. 3 is Li in examples 2 to 5 1.6 R x Mn 1.6-x O 4 An XRD pattern of (C) is shown in the figure. FIG. 4 is a cation-doped modified lithium ion sieve Li of example 2 1.6 Ni x Mn 1.6-x O 4 Is intended for TEM illustration. FIG. 7 is Li in examples 2 to 5 1.6 R x Mn 1.6-x O 4 Is intended to be an SEM illustration of (c).
As can be seen from XRD patterns, the original spinel structure is not changed by doping modification, and characteristic peak average corresponds to typical cubic phase Li 1.6 Mn 1.6 O 4 Spinel structure, FIG. 4 shows that the interplanar spacings of lattice planes shown in the HRTEM image are 0.476 and 0.247nm, compared with cubic Li 1.6 Mn 1.6 O 4 The inter-plane distances of the (111) and (311) lattice planes are consistent, and the inter-plane distance is slightly reduced after the crystal packet shrink doping, so that the material has high crystallinity and exists in a polycrystalline form. The SEM spectrogram is shown in figure 7 a, the particle size of the sample particles after doping modification is about 200nm, the primary particles are agglomerated into secondary particles, and the agglomerate is about 4-8 mu m.
Example 3
The preparation method of the cation doped modified lithium ion sieve comprises the following steps:
the first step: 2.45g of target doping element salt Co (NO 3 ) 2 ·6H 2 Dissolving O in 10mL ethanol by ultrasonic, slowly pouring 20g manganese carbonate into the solution after full dissolution, continuing ultrasonic treatment for 2 hours, drying for 12 hours at the temperature of 60 ℃, calcining for 5 hours at the temperature of 800 ℃ in air atmosphere, and heating at the temperature rising rate of 5 ℃/min during calcining to obtain the metal doped modified 14gMn 2-x Co x O 3 The method comprises the steps of carrying out a first treatment on the surface of the In the target doping element salt and the manganese salt, the molar ratio of Co to Mn is 0.05:1.
8.2g of metal-doped modified Mn 2-x Co x O 3 、5gLiOH·H 2 O was ground and mixed for 1 hour, mn 2-x Co x O 3 And a molar ratio of Li to Mn in the lithium salt of 1.15:1; fully reacting for 60 hours in a reaction kettle at 140 ℃ and centrifugally drying to obtain 11.08g LiMn 1-x Co x O 2 A powder;
and a second step of: 2g of LiMn obtained in the first step 1-x Co x O 2 Placing the powder into a corundum crucible, placing the corundum crucible into a muffle furnace, calcining for 24 hours at 500 ℃ in an air atmosphere, wherein the temperature rising rate is 5 ℃/min during calcining, and then naturally cooling to obtain the spinel type lithium ion sieve precursor 2.2gLi 1.6 Co x Mn 1.6-x O 4 (x=0.080) powder.
And a third step of: the lithium ion sieve precursor prepared in the second step is 0.1gLi 1.6 Co x Mn 1.6-x O 4 Soaking the powder in 0.1mol/L nitric acid 20mL for acidification treatment for 24h, eluting lithium ions in the precursor; and (3) carrying out suction filtration on the solution after the acidification treatment, washing the solution with deionized water for three times, and then drying the solution at 60 ℃ to obtain 0.1g of the cation doped modified lithium ion sieve.
The molecular formula of the cation doped modified lithium ion sieve is Li 1.6 Co x Mn 1.6-x O 4 ，x＝0.08。
XRD spectra of the product are shown in figures 2 and 3, and intermediate LiMn 1-x Co x O 2 The SEM spectra of (C) are shown in FIG. 5, FIG. 5 is LiMn of example 3 1-x Co x O 2 Is a schematic of SEM image.
From LiMn 1-x Co x O 2 And Li (lithium) 1.6 Co x Mn 1.6-x O 4 As can be seen from the XRD patterns of (a), the doped and modified sample and the orthorhombic LiMnO 2 With Li 1.6 Co x Mn 1.6-x O 4 The standard patterns of the (C) are consistent, and the doping modification does not change the crystal structures of the product and the intermediate, and has stronger peak intensity and good crystallinity. SEM spectrogram is shown in figure 7 b, and the morphology analysis is carried outThe particle size of the sample particles after doping modification is about 100-200nm, the primary particles are agglomerated into secondary particles, and the agglomerate is about 4-8 mu m.
Example 4
The preparation method of the cation doped modified lithium ion sieve comprises the following steps:
the first step: 1.26g of target doping element salt Cu (NO) 3 ) 2 ·6H 2 Dissolving O in 30mL ethanol by ultrasonic, slowly pouring 41g manganese acetate into the solution after full dissolution, continuing ultrasonic treatment for 2 hours, drying at 60 ℃ for 12 hours, calcining at 800 ℃ for 5 hours in air atmosphere, and obtaining metal doped modified Mn at a heating rate of 5 ℃/min during calcining 2-x Cu x O 3 The method comprises the steps of carrying out a first treatment on the surface of the In the target doping element salt and the manganese salt, the mol ratio of Cu to Mn is 0.03:1.
8.55g of metal-doped modified Mn 2-x Cu x O 3 、5gLiOH·H 2 O was ground and mixed for 3 hours, mn 2-x Cu x O 3 And a molar ratio of Li to Mn in the lithium salt of 1.1:1; fully reacting for 48 hours in a reaction kettle at the temperature of 140 ℃, and drying to obtain 11g of LiMn 1-x Cu x O 2 A powder;
and a second step of: 3g of LiMn obtained in the first step 1-x Cu x O 2 Placing the powder into a corundum crucible, placing the corundum crucible into a muffle furnace, calcining for 5 hours at 500 ℃ in an air atmosphere, wherein the temperature rising rate is 10 ℃/min during calcining, and then naturally cooling to obtain the spinel type lithium ion sieve precursor 3.3gLi 1.6 Cu x Mn 1.6-x O 4 (x=0.08) powder.
And a third step of: the lithium ion sieve precursor prepared in the second step is 0.1gLi 1.6 Cu x Mn 1.6-x O 4 Soaking the powder in 60mL of 0.3mol/L nitric acid for acidification treatment for 24h, eluting lithium ions in the precursor; and (3) carrying out suction filtration on the solution after the acidification treatment, washing the solution with deionized water for three times, and then drying the solution at 60 ℃ to obtain 0.1g of the cation doped modified lithium ion sieve.
Separation of the cation doped modified lithium ion sieveThe sub formula is Li 1.6 Cu x Mn 1.6-x O 4 ，x＝0.08。
The XRD spectrum of the product is shown in figure 3, and the TEM spectrum is shown in figure 6. FIG. 6 is LiMn in example 4 1-x Cu x O 2 Is a schematic of a TEM profile of (a). As can be seen from XRD patterns, the copper doping modification does not cause the occurrence of a hetero-phase, the original spinel structure is still maintained, the sample has good crystallinity from the peak shape, and the TEM pattern shows that the sample has a polycrystalline structure. The SEM spectrogram is shown in a graph c in fig. 7, and the morphology analysis shows that the particle size of most of the surface particles of the doped and modified sample is about 50-200nm, the primary particles are agglomerated into secondary particles, and the surface is smooth and the typical octahedral spinel structure can be seen.
Example 5
The preparation method of the cation doped modified lithium ion sieve comprises the following steps:
the first step: 3.6g of target doping element salt Zn (NO) 3 ) 2 ·6H 2 Dissolving O in 15mL ethanol by ultrasonic, slowly pouring 20g manganese carbonate into the solution after full dissolution, continuing ultrasonic treatment for 2 hours, drying for 12 hours at the temperature of 60 ℃, calcining for 5 hours at the temperature of 800 ℃ in air atmosphere, and heating at the temperature rising rate of 5 ℃/min during calcining to obtain 14g metal doped modified Mn 2-x Zn x O 3 The method comprises the steps of carrying out a first treatment on the surface of the In the target doping element salt and the manganese salt, the mol ratio of Zn to Mn is 0.07:1.
5g of metal-doped modified Mn 2-x Zn x O 3 、3gLiOH·H 2 O is ground and mixed for 2 hours, mn 2-x Zn x O 3 And a molar ratio of Li to Mn in the lithium salt of 1.15:1; fully reacting for 48 hours in a reaction kettle at 140 ℃ and centrifugally drying to obtain 6.04g of LiMn 1-x Zn x O 2 A powder;
and a second step of: 3g of LiMn obtained in the first step 1-x Zn x O 2 Placing the powder into a corundum crucible, placing the corundum crucible into a muffle furnace, calcining for 5 hours at 500 ℃ in an air atmosphere, wherein the temperature rising rate is 5 ℃/min during calcining, and then naturally cooling to obtain the spinel type lithium ion sieve precursor 3.27 and 3.27gLi 1.6 Zn x Mn 1.6-x O 4 (x=0.112) powder.
And a third step of: the lithium ion sieve precursor prepared in the second step is 0.1gLi 1.6 Zn x Mn 1.6-x O 4 Soaking the powder in 0.1mol/L nitric acid 20mL for acidification treatment for 24h, eluting lithium ions in the precursor; and (3) carrying out suction filtration on the solution after the acidification treatment, washing the solution with deionized water for three times, and then drying the solution at 60 ℃ to obtain 0.5g of the cation doped modified lithium ion sieve.
The molecular formula of the cation doped modified lithium ion sieve is Li 1.6 Zn x Mn 1.6-x O 4 ，x＝0.112。
The XRD spectrum of the product is shown in figure 3, and the SEM spectrum is shown in figure 7 d. As can be seen from an XRD graph, zinc doping modification does not cause the appearance of a hetero-phase, the original spinel structure is still maintained, the sample crystallinity is good from the peak shape, an SEM graph shows that the sample shape is octahedron, the particle size of the doped modified sample particle is about 200nm, primary particles are agglomerated into secondary particles, and the agglomerate is about 5-10 mu m.
Comparative example 1
Comparative example 1 differs from example 1 in that the doping element salt is not contained in the first step.
0.5g of the cation-doped modified lithium ion sieves of examples 2 to 5 and comparative example 1 were weighed respectively, put into 100ml of a 25mmol/L mixed ion solution, placed in a constant temperature shaking table, adsorbed for 48 hours at 25 ℃, and subjected to acid washing (hydrochloric acid time of 24 hours), and the ion concentration, manganese dissolution loss rate, desorption amount and adsorption capacity of the supernatant thereof were measured by ICP and the results are shown in Table 1.
Table 1 manganese dissolution loss, desorption amount and adsorption capacity of lithium ion sieves of different examples and comparative examples
| Loss rate of manganese (%) | Desorption amount (mg/g) | Adsorption capacity (mg/g) | |
| Example 1 | 0.4 | 61 | 46 |
| Example 2 | 0.3 | 60 | 47 |
| Example 3 | 0.1 | 62 | 45 |
| Example 4 | 0.4 | 65 | 43 |
| Example 5 | 0.7 | 68 | 44 |
| Comparative example 1 | 1.4 | 58 | 44 |
As can be seen from table 1: (1) Compared with Li before modification in comparative example 1 1.6 Mn 1.6 O 4 The R in the cation doped modified lithium ion sieve prepared by the invention is substituted for Mn to form a strong bond of R-Mn-O, and the adsorption capacity of the lithium ion sieve in the circulating process is increased, and the adsorption performance and the solubility resistance are improved; the cation doped modified lithium ion sieve prepared by the method has the advantages of high adsorption capacity, high selectivity and low manganese dissolution loss rate.
(2) The cation doped modified lithium ion sieve prepared by the method of the invention is pickled, and then lithium ion adsorption is carried out by salt lake brine, and the data in the table 1 can be combined to see that: the manganese dissolution loss rates of the cation-doped modified lithium ion sieves in examples 1-5 were respectively: 0.4%, 0.3%, 0.1%, 0.4%, 0.7% and desorption amounts are respectively: 61. 60, 62, 65 and 68mg/g, the adsorption amounts are respectively as follows: 46. 47, 45, 43, 44mg/g; the lithium ion sieve in comparative example 1 has a manganese dissolution loss rate of: 1.4%, the desorption amount is: 58mg/g and the adsorption capacity of 44mg/g, and the result shows that the cation doping effectively improves the stability of the adsorbent, reduces the manganese dissolution loss rate and improves the adsorption capacity. The method is beneficial to large-scale production and is applied to actual brine lithium extraction engineering.
Comparative example 2
Example 7 of the patent application publication No. CN103991908A serves as comparative example 2.
80.0mmol of lithium nitrate was dissolved in 20ml of deionized water, and 98.0mmol of manganese carbonate and 1.0mmol of cobalt trioxide were added. Placing in water bath at 80deg.C, stirring, and evaporating to dryness. Transferring the obtained mixture into a muffle furnace, calcining at 450 ℃ for 24 hours, cooling, and eluting in 1mol/l ammonium persulfate solution to obtain the ion sieve Mn 0.98 Co 0.02 O 2 ·0.31H 2 And the dissolution loss rate of the O and the manganese in the pickling process is only 0.7 percent.
Compared with comparative example 2, the method has lower manganese dissolution loss rate (the manganese dissolution loss rate of comparative example 2 is 0.7 percent, the manganese dissolution loss rate of the invention is 0.1 percent) and the adsorption and desorption amount are improved, and the reduction of the manganese dissolution loss rate is the key of the manganese-based adsorbent, so that the stability can be improved by reducing the manganese dissolution loss rate, and the use times and the application value of the adsorbent can be improved.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (7)
1. The preparation method of the cation doped modified lithium ion sieve is characterized by comprising the following steps of:
the first step: ultrasonically dissolving target doped element salt in a solvent, fully dissolving, slowly pouring manganese salt into the solvent, continuously ultrasonically treating the solution for 1 to 5 hours, drying the solution for 1 to 12 hours at the temperature of between 50 and 80 ℃, and calcining the solution for 3 to 12 hours at the temperature of between 500 and 800 ℃ in an air atmosphere to obtain metal doped modified Mn 2-x R x O 3 ；
Or mixing the target doping element salt and manganese salt uniformly, calcining for 3-12 h at 500-800 ℃ in air atmosphere to obtain metal doping modified Mn 2-x R x O 3 ；
In the target doping element salt and the manganese salt, the mol ratio of R to Mn is (0.01-0.18): 1;
doping metal modified Mn 2-x R x O 3 Grinding and mixing lithium salt, mn 2-x R x O 3 And a lithium salt wherein the molar ratio of Li to Mn is (1-1.2): 1; fully reacting for 1-72 hours at the temperature of 100-180 ℃, and drying to obtain LiMn 1-x R x O 2 A powder;
the target doping element salt is selected from acetate, sulfate, nitrate or carbonate of at least one Ti, fe, co, cu, ni, zn, zr, ce of the following elements;
the manganese salt is at least one selected from manganese acetate, manganese carbonate, manganese sulfate, manganese dioxide and manganese iodide;
the lithium salt is selected from LiOH.H 2 O、LiNO 3 Or Li (lithium) 2 CO 3 At least one of (a) and (b);
and a second step of: liMn obtained in the first step 1-x R x O 2 Calcining the powder for 4-72 h at 300-500 ℃ in air atmosphere to obtain lithium ion sieve precursor Li 1.6 R x Mn 1.6-x O 4 A powder;
and a third step of: lithium ion sieve precursor Li prepared in the second step 1.6 R x Mn 1.6-x O 4 Washing the powder with acid, filtering, washing with deionized water, and drying to obtain the cation doped modified lithium ion sieve Li 1.6 R x Mn 1.6-x O 4 ；
The molecular formula of the cation doped modified lithium ion sieve is Li 1.6 R x Mn 1.6-x O 4 R is selected from at least one of the following: ti, fe, co, cu, ni, zn, zr, ce, x is more than or equal to 0.01 and less than or equal to 0.25.
2. The method for preparing a cation-doped modified lithium ion sieve according to claim 1, wherein the salt of the target doping element in the first step is selected from Ni (NO 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·6H 2 O、Zn(NO 3 ) 2 ·6H 2 O、FeCl 3 。
3. The method of preparing a cation-doped modified lithium ion sieve of claim 1, wherein the solvent in the first step is selected from ethanol.
4. The method for preparing a cation-doped modified lithium ion sieve according to claim 1, wherein the temperature rising rate during the calcination in the first step is 1-10 ℃/min.
5. The method for preparing a cation-doped modified lithium ion sieve according to claim 1, wherein the temperature rising rate during the calcination in the second step is 1-10 ℃/min.
6. The method for preparing a cation-doped modified lithium ion sieve according to claim 1, wherein the acid in the third step is selected from hydrochloric acid, sulfuric acid or nitric acid.
7. The method for preparing a cation-doped modified lithium ion sieve according to claim 1, wherein the concentration of acid in the third step is 0.1-0.5 mol/L, and the soaking time is 24-48h.
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