CN-117486261-B - Iron ion doped ZrO2Preparation method of coated magnetic lithium ion sieve

Abstract

A preparation method of an iron ion doped ZrO 2 coated magnetic lithium ion sieve relates to a preparation method of a lithium ion sieve. The invention creatively provides a method for preparing the magnetic lithium ion sieve by adopting Fe 3+ doping and ZrO 2 cladding, and simultaneously reduces the dissolution loss of manganese and iron by adopting two methods of metal cation ion doping and cladding, thereby realizing high-efficiency solid-liquid separation, greatly prolonging the service life of the lithium ion sieve, and being applicable to extracting lithium from various lithium-containing solutions due to the acid and alkali resistance of ZrO 2 . The method comprises the steps of preparing FO, preparing LMFO, preparing ZrO 2 @ LMFO, and preparing ZrO 2 @ HMFO. The method has the advantages of simple process preparation, stable dissolution loss of manganese and iron after repeated recycling, good magnetic separation performance, suitability for mass production and contribution to promoting the industrialized development of extracting lithium from salt lake brine.

Inventors

• LI ZHENG
• LI WENKE
• SONG XIN
• LI LIANJIE
• LIU YUXIAO

Assignees

• 东北电力大学

Dates

Publication Date

20260508

Application Date

20231102

Claims (1)

1. 1. A preparation method of an iron ion doped ZrO 2 coated magnetic lithium ion sieve is characterized in that the saturation magnetization MS of the iron ion doped ZrO 2 coated magnetic lithium ion sieve prepared by the preparation method is 6.86emu/g, the iron ion doped ZrO 2 coated magnetic lithium ion sieve is adsorbed for 4 hours in LiCl solution with the concentration of 200mg/L and the volume of 100mL for basic balance, the adsorption amount is 35.8mg/g, the iron ion doped ZrO 2 coated magnetic lithium ion sieve is immersed into 40mL of hydrochloric acid with the concentration of 0.1mol/L for 3 hours, and the concentration of Mn 2+ 、Fe 3 +、Zr 4+ in the solution is only 2.8mg/L, 0.066mg/L and 0.013mg/L respectively; the preparation method is specifically completed by the following steps: 1. Preparation of FO: Dissolving 1.08g of ferric chloride hexahydrate in 40mL of ethylene glycol, carrying out ultrasonic treatment for 1h, adding 3g of sodium acetate, carrying out ultrasonic treatment for 1h to obtain a mixture, transferring the mixture into a reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 8h to obtain a precipitate, carrying out magnet separation on the precipitate, washing for 3 times by using deionized water and absolute ethyl alcohol respectively, sucking out a product by using a magnet, and drying at 60 ℃ to obtain nano Fe 3 O 4 which is marked as FO; 2. preparation LMFO: 1.1172g of LiOH.H256 and 0.12372g of FO are put into an agate mortar to be ground for 10min, then transferred into a corundum crucible, the corundum crucible is put into a muffle furnace, the muffle furnace is heated to 450 ℃, and then calcined for 4H at 450 ℃ to obtain a nano Fe 3 O 4 doped lithium ion sieve precursor which is marked as LMFO; the temperature rising rate of the muffle furnace in the second step is 5 ℃ per minute; 3. preparation of ZrO 2 @ LMFO: Adding 1g LMFO and 0.1g Zr (NO 3 ) 4 ·5H 2 O into 100mL deionized water, putting into a shaking table, shaking for 30min uniformly, drying at 80 ℃, transferring the dried powder into a corundum crucible, putting the corundum crucible into a muffle furnace, heating the muffle furnace to 450 ℃, and calcining at 450 ℃ for 2h to obtain a ZrO 2 coated magnetic lithium ion sieve precursor, which is denoted as ZrO 2 @ LMFO; the temperature rising rate of the muffle furnace in the third step is 5 ℃ per minute; 4. Preparation of ZrO 2 @ HMFO: 1g of ZrO 2 @ LMFO is put into 100mL of HCl solution with the concentration of 0.5mol/L, then the mixture is put into a shaking table, uniformly shaken and pickled for 8 hours, then suction-filtered, the obtained solid substance is washed to be neutral by deionized water, and then dried at 80 ℃ to obtain the iron ion doped ZrO 2 coated magnetic lithium ion sieve.

Description

Preparation method of iron ion doped ZrO 2 coated magnetic lithium ion sieve Technical Field The invention relates to a preparation method of a lithium ion sieve, in particular to a preparation method of an iron ion doped ZrO 2 coated magnetic lithium ion sieve. Background With the large-scale use of lithium ion batteries, the global demand for lithium resources has increased dramatically. At present, the extraction of lithium resources is mainly concentrated in salt lake brine, seawater and waste lithium ion battery liquid for extraction and recovery. The conventional lithium ion extraction and recovery method mainly comprises a precipitation method, a carbonization method, a solvent extraction method and an ion sieve adsorption method. The ion sieve adsorption method has the advantages of high selective adsorptivity, recycling regeneration, simple process flow, environmental friendliness and the like, is widely applied, and has great industrialization potential. The lithium ion sieve usually exists in a powder form and has the characteristics of poor fluidity, difficult recovery and the like. Shaping the lithium ion sieve can improve defects of the powdery ion sieve, such as granulating, membranous, fibrous, foam-like and the like. Although the stability of the granular lithium ion sieve is improved, the adsorption capacity is greatly reduced. The ion sieve membrane can also face the problem of membrane pollution and membrane damage. Although the ion sieve fiberization foaming can improve the adsorption quantity, the process of manufacturing materials is complex, and no related device and equipment for industrial production exist. The lithium ion sieve is magnetized, and a magnetic separation technology is utilized, so that high-efficiency solid-liquid separation is realized, and the method is a novel method for modifying the ion sieve. The method does not need complicated separation and recovery steps, not only remains the powder shape of the ion sieve, but also can more efficiently finish the separation and recovery of lithium ions. However, in the process of extracting lithium by using a magnetic lithium ion sieve, adsorption loss occurs, which is mainly due to the fact that manganese is easy to dissolve in the process of acidifying a precursor of the lithium ion sieve by hydrochloric acid, so that the development of industrialization of the lithium ion sieve is limited. Disclosure of Invention Aiming at the problems in the prior art, the invention creatively provides a method for preparing the magnetic lithium ion sieve by adopting Fe 3+ doping and combining ZrO 2 cladding, and simultaneously reduces the dissolution loss of manganese and iron by utilizing two methods of metal cation ion doping and cladding, thereby realizing high-efficiency solid-liquid separation, greatly prolonging the service life of the lithium ion sieve, and being applicable to extracting lithium from various lithium-containing solutions due to the acid-alkali resistance of ZrO 2. The technical scheme adopted by the invention is that the Fe 3+ doped ZrO 2 coated magnetic lithium ion sieve material is prepared, and is characterized in that the lithium ion sieve material with acid resistance and high circularity and easy solid-liquid separation is developed. Fe 3O4 is utilized to finish doping of Fe 3+, so that the lithium ion sieve is magnetized, and ZrO 2 is used for surface coating, so that the acid-base resistance and the dissolution loss resistance are formed. The invention discloses a preparation method of an iron ion doped ZrO 2 coated magnetic lithium ion sieve, which comprises the following steps: The preparation method of the iron ion doped ZrO 2 coated magnetic lithium ion sieve is specifically completed by the following steps: 1. Preparation of FO: Dissolving ferric chloride hexahydrate in glycol, performing ultrasonic treatment, adding sodium acetate, performing ultrasonic treatment to obtain a mixture, transferring the mixture into a reaction kettle, performing hydrothermal reaction at 200 ℃ for a period of time to obtain a precipitate, performing magnet separation on the precipitate, washing, and drying to obtain nano Fe 3O4, and marking as FO; 2. preparation LMFO: Grinding LiOH.H 2O、MnO2 and FO in an agate mortar, transferring to a corundum crucible, putting the corundum crucible into a muffle furnace, heating the muffle furnace to 400-450 ℃, and calcining at 400-450 ℃ for a period of time to obtain a nano Fe 3O4 doped lithium ion sieve precursor which is marked as LMFO; 3. preparation of ZrO 2 @ LMFO: Adding LMFO and Zr (NO 3)4·5H2 O) into deionized water, putting into a shaking table, shaking for a period of time uniformly, drying, transferring the dried powder into a corundum crucible, putting the corundum crucible into a muffle furnace, heating the muffle furnace to 400-450 ℃, and calcining at 400-450 ℃ for a period of time to obtain a ZrO 2 coated magnetic lithium ion sieve precursor, which is denoted as ZrO 2