Lithium ion sieve taking waste lithium manganate battery material as raw material, and preparation method thereof

Abstract

The invention relates to a lithium ion sieve taking a waste lithium manganate battery material as a raw material, and a preparation method thereof, and especially relates to an aluminum-doped manganese lithium ion sieve filler loaded on an aluminum oxide carrier. The chemical composition of the lithium ion sieve is H1.33Alx Mn1.67O4.yAl2O3, wherein x is equal to 0.03-0.33, and y is equal to 0.06-0.18. The preparation method comprises the following steps: mixing a pretreated waste lithium manganate battery positive electrode material with LiOH, roasting at high temperature to form a precursor, and further delithiating with diluted hydrochloric acid to obtain the lithium ion sieve. In a 0.5 g / L lithium chloride aqueous solution, the lithium ion recovery rate is 95-98%, the adsorption capacity of the lithium ion sieve is 48-54 mg / g, the adsorption capacity change is less than 1% after 10 times of adsorption and desorption, and the dissolution loss is less than 1%. The lithium ion sieve is large in adsorption capacity, high in adsorption and desorption speed, low in production cost and stable in application performance, has industrial application prospects and is suitable for adsorbing and extracting lithium in a low-concentration lithium-containing aqueous solution.

Description

technical field [0001] The invention relates to a lithium ion sieve using waste lithium manganese oxide battery material as a raw material and a preparation method thereof, which is used for absorbing and extracting lithium from a low-concentration lithium-containing aqueous solution, and belongs to the fields of chemical industry and new energy materials. [0002] technical background [0003] China is the world's largest producer, consumer and exporter of lithium-ion batteries. The demand for lithium salt continues to grow rapidly. The existing production capacity of lithium salt is more than 200,000 tons, which still cannot meet the growing market demand. Lithium in nature is stored in seawater, salt lake brine and granite-type deposits. China's lithium ore resource reserves are low, the concentration of magnesium in salt lake brine is high, and the production technology of lithium salt is difficult. [0004] With the explosive growth of lithium-ion battery scrap, people'...

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Problems solved by technology

[0008] Chinese patent CN108199104A (2018-06-22) discloses a method for preparing a lithium ion sieve from lithium manganate battery waste and its lithium ion sieve, directly impregnating lithium manganate waste with acid, dissolving and removing aluminum, and obtaining a lithium-containing solution and a lithium ion sieve. Ion sieve, but the adsorption capacity of lithium ion sieve obtained by this method is only 25mg / g, and the manganese loss rate during dilute acid delithiation is as high as 5%-10%

Chinese patent CN110474122A (2019-11-19) changed the preparation conditions of lithium manganate battery waste to prepare lithium ion sieves, and used alkaline solution to remove aluminum impurities in the raw materials, and carried out lithium supplementation operation in the preparation of lithium ion sieves , the obtained lithium ion adsorption capacity is only about 15mg / g, but the manganese loss rate is reduced to about 5%.

The adsorption capacity and cycle life of the lithium ion sieve obtained by the above method cannot meet the practical requirements, and the recovery rate of lithium and manganese cannot reach 85% and 95% of the industry standard requirements.

In addition, the powdered lithium ion sieve obtained by the above method is not suitable for industrial application, and the subsequent molding process will further reduce the adsorption capacity of lithium ion sieve