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固相法合成鈷摻雜錳系鋰離子篩的吸附性能

Lithium adsorption performance of Co-doped manganese-based lithium-ion sieves prepared via solid-phase synthesis

  • 摘要: 隨著5G/6G通信、新能源汽車、鋰電池產業的快速發展,近年來對鋰化合物(尤其是Li2CO3)的需求急劇增加,許多國家將鋰視為戰略礦產資源. 目前從鋰沉淀母液中提取鋰受到了極大的關注. 錳系離子篩(LMO)是一種具有廣泛應用前景的吸附劑,可實現復雜溶液中鋰的高效回收. 但LMO在酸洗解吸過程中存在錳溶損嚴重的難題,會降低吸附性能和循環性能. 針對上述問題,本研究提出引入Co3+摻雜降低LMO錳溶解損失的策略,制備了鈷摻雜錳系離子篩(LCMO). 采用X射線衍射(XRD)、掃描電子顯微鏡(SEM)、透射電子顯微鏡(TEM)、X射線光電子能譜(XPS)等方法對不同煅燒溫度和焙燒時間下制備的LCMO進行表征分析. 表征結果表明,Co摻雜對LMO的尖晶石結構沒有影響,并且Co最佳摻雜摩爾分數為5%,此時離子篩前驅體中Mn3+的原子分數從未摻雜的9.67%降低到3.63%,對應的鋰吸附容量從39.299 mg·g?1顯著增加到41.708 mg·g?1,錳溶損也從1.288%顯著降低至0.837%,大大地增加了錳系離子篩的實際應用可能性. 制備的摩爾分數為5%Co摻雜的離子篩(LCMO-5%)具有良好的循環性能,Li+的吸附能力在5次循環后仍然保持在81%以上. 在模擬的鋰沉淀母液中,Li/Na和Li/K之間的分離系數分別為74.655和64.547,這證明了LCMO-5%能有效地從高Na+、K+溶液中吸附分離Li+. 因此,LCMO-5%離子篩具有從鋰沉淀母液中提取Li+的應用前景.

     

    Abstract: With the rapid development of 5G/6G communications, new energy vehicles, and lithium battery industries, the demand for lithium compounds (especially Li2CO3) has dramatically increased in recent years. Many countries have regarded lithium as a strategic mineral resource. Lithium is mainly found in liquid mineral resources around the world, and the extraction of lithium from the mother liquor of lithium precipitates has thus garnered significant attention. The main methods for recovering lithium from solutions include membrane separation, solvent extraction, electrochemistry, and adsorption. Among them, the adsorption method is one of the most promising. The key to successful adsorption technology is the construction of high-performance adsorbents with high adsorption capacity, high ionic selectivity, and high structural stability. The manganese-ion sieve named as LMO, is a promising adsorbent that has been widely studied because of its good chemical stability, excellent adsorption properties, and outstanding ion selectivity for lithium extraction. However, its inherent dissolution loss greatly restricts its practical application. To reduce the dissolution loss of manganese-ion sieves, several strategies, such as adjusting the synthesis process, composition optimization, ion doping, and surface modification, were adopted. This study introduces Co3+ doping to mitigate manganese loss in LMO, resulting in the preparation of cobalt-doped manganese-based ion sieves (LCMO). LCMOs prepared at various calcination temperatures and times were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy, and X-ray photoelectron spectroscopy (XPS). The XRD characterization results indicate that Co doping has no effect on the spinel structure of LMO. The SEM results confirmed the successful doping and uniform Co distribution in LCMO-5%. The XPS results show that a Co doping molar fraction of 5% can reduce the content of Mn3+ from 9.67% in the undoped precursor to 3.63%, which may be because the partial substitution of Mn3+ by Co3+ reduces the proportion of Mn3+. The lithium adsorption capacity increased from 39.299 to 41.708 mg·g?1, and the manganese dissolution significantly decreased from 1.288% to 0.84%. The performance improvement of the LCMO greatly promotes the practical application of manganese-based ion sieves. The prepared 5% molar fraction of the Co-doped ion sieve (LCMO-5%) exhibited excellent cycling performance, and the adsorption efficiency of Li+ remained above 81% after five cycles. In the simulated lithium precipitation mother liquor, the separation coefficients of Li/Na and Li/K were 74.655 and 64.547, respectively, indicating that LCMO-5% effectively adsorbed Li+ from solutions containing high concentrations of Na+ and K+. Therefore, the LCMO-5% ion sieve exhibits outstanding application prospects for Li+ extraction from liquid lithium resources.

     

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