CN112777643A - Mg-doped modified lithium ion sieve and preparation method thereof - Google Patents
Mg-doped modified lithium ion sieve and preparation method thereof Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical class [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 239000011572 manganese Substances 0.000 claims abstract description 52
- 239000011777 magnesium Substances 0.000 claims abstract description 44
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 12
- 239000011029 spinel Substances 0.000 claims abstract description 12
- 229910001868 water Inorganic materials 0.000 claims abstract description 12
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002993 LiMnO2 Inorganic materials 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 230000020477 pH reduction Effects 0.000 claims abstract description 6
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 239000011656 manganese carbonate Substances 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
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910014689 LiMnO Inorganic materials 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 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
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 25
- 229910052748 manganese Inorganic materials 0.000 abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 13
- 238000004090 dissolution Methods 0.000 abstract description 12
- 239000002253 acid Substances 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910011981 Li4Mn5O12 Inorganic materials 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- 229910013068 LiMxMn2-xO4 Inorganic materials 0.000 description 1
- 229910013064 LiMxMn2−xO4 Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1285—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O5]n-
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Analytical Chemistry (AREA)
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- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of a Mg-doped modified lithium ion sieve, which comprises the following steps: s01: dissolving lithium salt, manganese oxide and magnesium salt in water, and placing the solution in a reaction kettle to be fully stirred for 10-18 hours; wherein the temperature in the reaction kettle is 150-300 ℃; centrifugally drying the product after reaction to obtain LiMnO2-Mg powder; s02: mixing the LiMnO2Calcining the-Mg powder at 200-500 ℃ for 4-12 hours to obtain Li1.6MgxMn1.6‑xO4Powder; s03: mixing Li1.6MgxMn1.6‑xO4Soaking the powder in inorganic acid for acidification; and centrifugally drying the acidified solution to obtain the Mg-doped modified lithium ion sieve. The Mg-doped modified lithium ion sieve is a single pure-phase spinel crystal form. The present invention providesThe Mg-doped modified lithium ion sieve has high adsorption capacity and excellent stability, and the manganese dissolution loss rate is effectively reduced in the acid washing process.
Description
Technical Field
The invention relates to the field of ionic sieves, and particularly belongs to a Mg-doped modified lithium ionic sieve and a preparation method thereof.
Background
In the past decades, the demand for new energy sources has been rising due to the growth of the world population and the advancement of scientific technology. By means of the characteristics of lightness and smallness of lithium metal and ions, the lithium battery becomes one of energy storage devices with the highest specific energy density, and is widely applied to the field of various new energy sources. The strong development of the new energy industry promotes the rise of the demand of lithium resources. Lithium resources exist in natural minerals (spodumene, clay, etc.), salt lake brine and seawater, and among these lithium resources, continental brine resources account for the largest proportion except for seawater. It is important to separate and extract lithium ions from these resources for ten minutes. The inorganic separation material comprises manganese oxide ion sieve adsorbents and titanium oxide ion sieve adsorbents which take ion exchange reaction as an adsorption mechanism, manganese oxide materials and iron phosphate materials which take electrochemical reaction as a separation mechanism, and aluminum adsorbents which absorb lithium chloride molecules. Of these materials, oxides of manganese in Li+High adsorption capacity and Li in extraction process+And (4) selectivity. In all LMO spinel materials, Li1.6Mn1.6O4Most representative from the viewpoint of stability after several cycles and higher theoretical adsorption capacity.
However, the dissolution loss of manganese not only reduces the adsorption capacity but also pollutes raw water and desorption liquid in practical use. Thus, a key problem in practical applications is the substantial dissolution of manganese during desorption. Doping modification is considered to be the simplest and most effective way to increase the manganese dissolution loss of the spinel sorbent. The main purpose of introducing the foreign ions is to increase the average valence of manganese in the lithium manganate spinel while reducing the Mn3+Or to enhance octahedral chemical bonds.
Ma et al prepared a series of LiMxMn2-xO4(M ═ Ni, Al, Ti; 0. ltoreq. x.gtoreq.1) spinel adsorbents and their lithium ion recovery performance in aqueous solution were compared. The results show that LiAl is present during the acid treatment0.5Mn1.5O4Exhibits a high Li + adsorption rate, while Mn and Al have low dissolution rates, and LiNi0.5Mn1.5O4And LiTi0.5Mn1.5O4Showing a weaker Li + adsorption performance. However, doping modification of LMO is mainly focused on LiMn2O4And Li4Mn5O12To Li1.6Mn1.6O4There are few studies.
Disclosure of Invention
The Mg-doped modified lithium ion sieve provided by the invention has high adsorption capacity and excellent stability, and effectively reduces the manganese dissolution rate in the acid washing process.
In order to achieve the purpose, the invention adopts the following technical scheme: the molecular formula of the Mg-doped modified lithium ion sieve is Li1.6MgxMn1.6-xO4Wherein x is more than or equal to 0.032 and less than or equal to 0.128; the Mg-doped modified lithium ion sieve is in a spinel crystal form.
Further, the method comprises the following steps:
s01: dissolving lithium salt, manganese oxide and magnesium salt in water, and placing the solution in a reaction kettle to be fully stirred for 10-18 hours; wherein the temperature in the reaction kettle is 150-300 ℃; centrifugally drying the product after reaction to obtain LiMnO2-Mg powder;
s02: mixing the LiMnO2Calcining the-Mg powder at 200-500 ℃ for 4-12 hours to obtain Li1.6MgxMn1.6- xO4Powder;
s03: mixing Li1.6MgxMn1.6-xO4Soaking the powder in inorganic acid for acidification; and centrifugally drying the acidified solution to obtain the Mg-doped modified lithium ion sieve.
Further, in the step S01, the manganese oxide is Mn2O3(ii) a The magnesium salt is any one of magnesium acetate, magnesium carbonate, magnesium sulfate or magnesium nitrate, and the lithium salt is LiOH & H2O, LiOH or Li2CO3Any one of the above.
Further, in the step S01, the molar ratio of Li to Mn in the lithium salt and the manganese oxide is 2.5-5: 1; the molar ratio of Mg/Mn in the magnesium salt and the manganese oxide is 0-0.1: 1.
Further, in the step S01, the manganese oxide is obtained by roasting manganese salt in an air atmosphere.
Further, the manganese salt is any one of manganese acetate, manganese sulfate or manganese carbonate.
Further, the inorganic acid is hydrochloric acid or sulfuric acid or nitric acid, the concentration of the inorganic acid is 0.1-0.5 mol/L, and the soaking time is 24-48 h.
Further, the temperature rise rate is controlled to be 2-5 ℃/min until the preset calcination temperature is reached when the calcination is carried out in the step S02, wherein the preset calcination temperature is 200-500 ℃; calcining at the preset calcining temperature for 4-12 hours.
Further, the temperature in the reaction kettle in the step S01 is 210-250 ℃.
Further, LiMnO in the step S022The R powder is calcined at a temperature of 350-450 ℃ for 4-12 hours.
The invention has the following beneficial effects: the Mg-doped modified lithium ion sieve has high adsorption capacity and high lithium ion selectivity, which is attributed to Li of the Mg-doped modified lithium ion sieve1.6MgxMn1.6-xO4A characteristic rigid crystal structure; in addition, the stability is strong, and the composite material can be used for repeated recycling; finally, the manganese dissolution loss rate is low; the method of the invention is conducive to large-scale manufacturing and application.
Drawings
FIG. 1 shows Mg-doped modified Li-ion sieve in example 11.6Mn1.6O4-XRD pattern of R;
FIG. 2 shows an exampleMg-doped modified lithium ion sieve Li in 11.6Mn1.6O4-SEM picture of R;
FIG. 3 shows Mg-doped modified Li-ion sieve in example 11.6Mn1.6O4TEM image of R.
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.
The invention provides a Mg-doped modified lithium ion sieve, the molecular formula of which is Li1.6MgxMn1.6-xO4Wherein x is more than or equal to 0.032 and less than or equal to 0.128; the Mg-doped modified lithium ion sieve is a single pure-phase spinel crystal form.
Example 1
A method for preparing Mg doped modified lithium ion sieve comprises the following steps:
s01: taking MnCO3Roasting at 800 ℃ for 5h in air atmosphere to obtain Mn2O3(ii) a Adding Mn2O3、LiOH·H2O and Mg (NO)3)2Dissolving in water, placing in a reaction kettle, and fully stirring for 12 hours; wherein the temperature in the reaction kettle is 230 ℃; centrifugally drying the product after reaction to obtain LiMnO2-Mg powder;
in the step, the molar ratio of Li to Mn is 4: 1; the molar ratio of Mg/Mn in the magnesium salt and the manganese oxide is 0.05: 1.
S02: mixing LiMnO2Putting Mg powder into a corundum crucible, putting the corundum crucible into a muffle furnace, calcining for 5 hours at 400 ℃ in air atmosphere, and naturally cooling to obtain a spinel type lithium ion sieve precursor Li1.6MgxMn1.6-xO4And (3) powder.
S03: mixing Li1.6MgxMn1.6-xO4Soaking the powder in 0.3mol/L HCl for acidification for 36 h; and centrifugally drying the acidified solution to obtain the Mg-doped modified lithium ion sieve.
FIG. 1 shows Mg-doped modified lithium in example 1Ion sieve Li1.6MgxMn1.6-xO4The XRD pattern of (a) can be seen: finally formed Mg-doped modified lithium ion sieve Li1.6MgxMn1.6-xO4The strong diffraction peak of (a) shows good crystallinity, indicating that the spinel structure is maintained after doping modification. The position of the diffraction peak is slightly shifted toward the lower 2 θ angle as the Mg content increases. Mg (magnesium)2+Has a radius of
Greater than Mn3+Radius of (2)
FIG. 2 and FIG. 3 show Mg-doped modified Li-ion sieve in example 11.6MgxMn1.6-xO4SEM and TEM images of the same, it can be observed in fig. 2 that LMMO-6% and LMO have similar morphologies. The particle size in LMO and LMMO-6% is several microns, and the particle size is composed of smaller flaky particles with the diameter of about 100nm, and the morphology is more favorable for adsorption performance. The high resolution tem (hrtem) image in fig. 3 shows that this sample has good crystallinity.
Example 2
A method for preparing Mg doped modified lithium ion sieve comprises the following steps:
s01: taking MnSO4Roasting at 800 ℃ for 5h in air atmosphere to obtain Mn2O3(ii) a Adding Mn2O3、LiOH·H2O and Mg (NO)3)2Dissolving in water, placing in a reaction kettle, and fully stirring for 12 hours; wherein the temperature in the reaction kettle is 150 ℃; centrifugally drying the product after reaction to obtain LiMnO2-Mg powder;
in the step, the molar ratio of Li to Mn is 2.5: 1; the molar ratio of Mg/Mn in the magnesium salt and the manganese oxide is 0.01: 1.
S02: mixing LiMnO2-Mg powder is placed in a corundum crucible and the corundum crucible is placed in a muffle furnace and calcined at 200 ℃ for 5 hours in an air atmosphere, followed by natural cooling, i.e.Obtaining a spinel type lithium ion sieve precursor Li1.6MgxMn1.6-xO4And (3) powder.
S03: mixing Li1.6MgxMn1.6-xO4Soaking the powder in 0.1mol/L sulfuric acid for acidification treatment for 24 h; and centrifugally drying the acidified solution to obtain the Mg-doped modified lithium ion sieve.
Example 3
A method for preparing Mg doped modified lithium ion sieve comprises the following steps:
s01: manganese acetate is taken and roasted for 5h at 800 ℃ in air atmosphere to obtain Mn2O3(ii) a Adding Mn2O3、LiOH·H2O and Mg (NO)3)2Dissolving in water, placing in a reaction kettle, and fully stirring for 12 hours; wherein the temperature in the reaction kettle is 300 ℃; centrifugally drying the product after reaction to obtain LiMnO2-Mg powder;
in the step, the molar ratio of Li to Mn is 5: 1; the molar ratio of Mg/Mn in the magnesium salt and the manganese oxide is 0.1: 1.
S02: mixing LiMnO2Putting Mg powder into a corundum crucible, putting the corundum crucible into a muffle furnace, calcining for 5 hours at 500 ℃ in air atmosphere, and naturally cooling to obtain a spinel type lithium ion sieve precursor Li1.6MgxMn1.6-xO4And (3) powder.
S03：Li1.6MgxMn1.6-xO4Soaking the powder in 0.1mol/L nitric acid for acidification treatment for 24 h; and centrifugally drying the acidified solution to obtain the Mg-doped modified lithium ion sieve.
Comparative example 1
Comparative example 1 differs from example 1 in that no magnesium salt is included in step S01.
Experimental example 1
0.1g of the Mg-doped modified lithium ion sieves of examples 1 to 3 and comparative example 1 were weighed into 20ml of Li-containing sieves, respectively+The adsorption capacity of 165mg/L salt lake brine after 48 hours of adsorption at 25 ℃ is shown as the first adsorption capacity in Table 1;the lithium ion sieve after absorbing lithium ions can be reused after being washed by inorganic acid, the experiment example continues to test the adsorption capacity of the lithium ion sieve after being washed by acid for the fifth time and the tenth time, and the test method is the same as the test method of the adsorption capacity for the first time.
TABLE 1 adsorption capacities of lithium ion sieves of the different examples and comparative examples
It can be seen that: (1) compared with the pure lithium ion sieve in the comparative example 1, the adsorption capacity of the Mg-doped modified lithium ion sieve prepared by the invention to lithium ions is greatly increased; the Mg-doped modified lithium ion sieve prepared by the method is high in adsorption capacity and high in lithium ion selectivity.
(2) The Mg-doped modified lithium ion sieve prepared by the method is subjected to acid washing after being used, and the Mg-doped modified lithium ion sieve subjected to acid washing can continuously perform lithium ion adsorption; as can be seen in conjunction with table 1 above: in examples 1-3, the adsorption capacity of the Mg-doped modified lithium ion sieve is kept at about 72% after 5 times of circulation, and the adsorption capacity is kept at about 60% after 10 times of circulation; in the comparative example, the adsorption capacity of the lithium ion sieve is kept at about 60% after 5 times of circulation, and the adsorption capacity of the lithium ion sieve is kept at about 40% after 10 times of circulation, so that the retention rate of the adsorption performance of the lithium ion sieve is obviously inferior to that of the Mg-doped modified lithium ion sieve prepared by the method.
Experimental example 2
The lithium ion sieves of examples 1 to 3 and comparative examples were tested for manganese dissolution loss by the following method: 0.1g of the Mg-doped modified lithium ion sieves of examples 1 to 3 and comparative example 1 was weighed into 20ml of a Li-containing sieve+Absorbing the lithium ion sieve in 165mg/L salt lake brine at 25 ℃ for 48 hours, then carrying out acid washing on the lithium ion sieve, taking supernate after the acid washing process, and testing residual Mn by using an atomic absorption spectrometer or ICP (inductively coupled plasma)2+The test results are shown in table 2.
TABLE 2 manganese dissolution loss amounts of lithium ion sieves of different examples and comparative examples
| Manganese dissolution loss (%) | |
| Example 1 | 2.9 |
| Example 2 | 3.12 |
| Example 3 | 3.04 |
| Comparative example 1 | 3.69 |
It can be seen that the manganese dissolution loss of the Mg-doped modified lithium ion sieve prepared by the present invention is significantly lower than that of the pure lithium ion sieve in comparative example 1.
The Mg-doped modified lithium ion sieve has high adsorption capacity and high lithium ion selectivity, which is attributed to Li of the Mg-doped modified lithium ion sieve1.6MgxMn1.6-xO4A characteristic rigid crystal structure; in addition, the stability is strong, and the composite material can be used for repeated recycling; finally, the manganese dissolution loss rate is low; the method of the invention is conducive to large-scale manufacturing and application.
The above description is only a preferred embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, so that all equivalent structural changes made by using the contents of the specification and the drawings of the present invention should be included in the scope of the appended claims.
Claims (10)
1. The Mg-doped modified lithium ion sieve is characterized in that the molecular formula of the Mg-doped modified lithium ion sieve is Li1.6MgxMn1.6-xO4Wherein x is more than or equal to 0.032 and less than or equal to 0.128; the Mg-doped modified lithium ion sieve is in a spinel crystal form.
2. A method of preparing the Mg-doped modified lithium ion sieve of claim 1, comprising the steps of:
s01: dissolving lithium salt, manganese oxide and magnesium salt in water, and placing the solution in a reaction kettle to be fully stirred for 10-18 hours; wherein the temperature in the reaction kettle is 150-300 ℃; centrifugally drying the product after reaction to obtain LiMnO2-Mg powder;
s02: mixing the LiMnO2Calcining the-Mg powder at 200-500 ℃ for 4-12 hours to obtain Li1.6MgxMn1.6-xO4Powder;
s03: mixing Li1.6MgxMn1.6-xO4Soaking the powder in inorganic acid for acidification; and centrifugally drying the acidified solution to obtain the Mg-doped modified lithium ion sieve.
3. The method as claimed in claim 2, wherein the manganese oxide in step S01 is Mn2O3(ii) a The magnesium salt is any one of magnesium acetate, magnesium carbonate, magnesium sulfate or magnesium nitrate, and the lithium salt is LiOH & H2O, LiOH or Li2CO3Any one of the above.
4. The method of claim 2, wherein the molar ratio of Li/Mn in the lithium salt and the manganese oxide in step S01 is 2.5-5: 1; the molar ratio of Mg/Mn in the magnesium salt and the manganese oxide is 0.01-0.1: 1.
5. The method of claim 2, wherein the manganese oxide is obtained by calcining a manganese salt in an air atmosphere in step S01.
6. A method as claimed in claim 5, wherein the manganese salt is any one of manganese acetate, manganese sulfate, or manganese carbonate.
7. A preparation method according to claim 2, characterized in that the inorganic acid is hydrochloric acid or sulfuric acid or nitric acid, the concentration of the inorganic acid is 0.1 mol/L-0.5 mol/L, and the soaking time is 24-48 h.
8. The method as claimed in claim 2, wherein the temperature raising rate is controlled to be 2-5 ℃/min until a preset calcination temperature is reached in the calcination in step S02, and the preset calcination temperature is 200-500 ℃; calcining at the preset calcining temperature for 4-12 hours.
9. The method as claimed in claim 2, wherein the temperature in the reaction vessel in step S01 is 210-250 ℃.
10. A production method according to claim 2, wherein LiMnO in step S02 is LiMnO2The R powder is calcined at a temperature of 350-450 ℃ for 4-12 hours.
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| CN116371387A (en) * | 2023-02-28 | 2023-07-04 | 华东理工大学 | Preparation method of cation doped modified lithium ion sieve |
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Non-Patent Citations (3)
| Title |
|---|
| GAIFANG CAO等: ""Synthesis, Adsorption Properties and Stability of Cr-Doped Lithium Ion Sieve in Salt Lake Brine"", 《BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN》 * |
| RAMESH CHITRAKAR等: ""Magnesium-Doped Manganese Oxide with Lithium Ion-Sieve Property: Lithium Adsorption from Salt Lake Brine"", 《BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN》 * |
| 钱方仁等: "Mg2+掺杂对H1.6M1.6O4锂离子筛吸附性能的影响", 《盐湖研究》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116371387A (en) * | 2023-02-28 | 2023-07-04 | 华东理工大学 | Preparation method of cation doped modified lithium ion sieve |
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