Preparation methods and analyses of structural performance of spinel-type lithium manganese oxide ion sieves

doi:10.16085/j.issn.1000-6613.2015.06.030

Abstract

Abstract: As a type of adsorbents for extracting lithium from solution, spinel-type lithium manganese oxides are the most promising ones for the industrial application of lithium. However, there still exist several problems in the process of practical research and application. The comparison of preparation methods for three types of lithium manganese oxide ion sieve precursors ( LiMn₂O₄、Li₄Mn₅O₁₂and Li_1.6Mn_1.6O₄) and corresponding ion sieves ( λ-MnO₂、MnO₂·0.31H₂O and MnO₂·0.5H₂O) were introduced in detail. The distinction of crystal structures and characteristics for the precursors and adsorption capabilities for the ion sieves were analyzed emphatically. Moreover, the granule/membrane formation of powder lithium ion sieves and their application were summarized, and the difference of adsorption capacities among three forms of lithium ion sieves was also elaborated. Finally, the difference of adsorption capabilities in theory and practice, selectivity and dissolved loss for lithium ion sieves were summed up in detail, meanwhile, the ion sieve adsorbents for extraction lithium from seawater could realize industrial application with the improvement of molding technology for powder ion sieves and the development of novel and doped lithium ion sieves.

Key words: lithium ion sieves, adsorbents, extraction, crystal structure, granulation, membrane formation

摘要： 尖晶石型锂锰氧化物离子筛作为一种溶液提锂的吸附材料, 具有广阔的应用前景, 而在实际研究与推广应用进程中, 也存在着一些问题。文章结合已有的研究, 详细介绍了目前研究最多的三种锂锰氧化物离子筛前体(LiMn₂O₄、Li₄Mn₅O₁₂和 Li_1.6Mn_1.6O₄)和对应锰氧化物离子筛(λ-MnO₂、MnO₂·0.31H₂O和MnO₂·0.5H₂O)制备方法的比较;重点分析了三种前体和离子筛的晶体结构特征以及离子筛吸附性能的本质区别;对粉状离子筛的成型(造粒和成膜)作了详细阐述并与粉状离子筛的性能进行了比较;最后总结了目前锂锰氧化物离子筛实际吸附量与理论吸附量的差异和选择性以及离子筛溶损等现存的问题。随着离子筛成型技术的改善和掺杂新型离子筛的开发, 有望制备工业化应用的海水提锂吸附剂。

关键词: 锂离子筛, 吸附剂, 提取, 晶体结构, 造粒, 成膜

CLC Number:

TB34

YANG Shanshan, RUAN Huimin, SHEN Jiangnan, GAO Congjie. Preparation methods and analyses of structural performance of spinel-type lithium manganese oxide ion sieves[J]. Chemical Industry and Engineering Progree, 2015, 34(06): 1690-1698,1736.

杨珊珊, 阮慧敏, 沈江南, 高从堦. 尖晶石型锂锰氧化物离子筛的制备方法及构效性能分析[J]. 化工进展, 2015, 34(06): 1690-1698,1736.

References

[1] Kesler S E, Gruber P W, Medina P A, et al. Global lithium resources:Relative importance of pegmatite, brine and other deposits[J]. Ore Geology Reviews, 2012, 48:55-69.
[2] 戴自希. 世界锂资源现状及开发利用趋势[J]. 中国有色金属, 2008, 8(4):17-20.
[3] 纪志永, 许长春, 袁俊生, 等. 尖晶石型锂离子筛研究进展[J]. 化工进展, 2005, 24(12):1336-1341.
[4] 肖小玲, 戴志峰, 祝增虎, 等. 吸附法盐湖卤水提锂的研究进展[J]. 盐湖研究, 2005, 13(2):66-69.
[5] 董殿权, 刘维娜, 刘亦凡. 二氧化锰型钾离子筛的合成及其对钾的离子交换热力学[J]. 化工进展, 2009, 28(6):1005-1009.
[6] 李丽, 刘芳, 吴锋, 等. 提锂用锰氧化物离子筛的研究进展[J]. 无机材料学报, 2012, 27(10):1009-1016.
[7] 周燕芳, 钟辉. 尖晶石LiMn₂O₄正极材料的研究进展[J]. 化工进展, 2003, 22(2):140-145.
[8] 王大伟. 离子筛法海水提锂新工艺研究[D]. 天津:河北工业大学, 2008.
[9] Sato K, Poojary D M, Clearfield A. The surface structure of the proton-exchanged lithium manganese oxide spinels and their lithium-ion sieve properties[J]. Journal of Solid State Chemistry, 1997, 131:84-93.
[10] 许惠, 卓琳. 锂离子筛前驱体LiMn₂O₄的制备及锂吸附性能研究[J]. 化工新型材料, 2013, 41(8):123-125.
[11] Özgür C. Preparation and characterization of LiMn₂O₄ion-sieve with high Li⁺adsorption rate by ultrasonic spray pyrolysis[J]. Solid State Ionics, 2010, 181:1425-1428.
[12] Zhang Q H, Sun S Y, Li S P, et al. Adsorption of lithium ions on novel nanocrystal MnO₂[J]. Chemical Engineering Science, 2007, 62:4869-4874.
[13] 王英平, 王先友, 隗小山, 等. 以Mn₃O₄为前驱体制备尖晶石型LiMn₂O₄及其性能[J]. 中国有色金属学报, 2012, 22(8):2276-2282.
[14] 李有坤, 邱克辉. 尖晶石型LiMn₂O₄的凝胶燃烧法制备[J]. 功能材料, 2013, 44(4):498-501, 506.
[15] 许惠, 陈昌国, 宋应华. 锂离子筛前驱体Li₄Mn₅O₁₂的制备及性能研究[J]. 无机材料学报, 2013, 28(7):720-726.
[16] Sun S Y, Song X F, Zhang Q H, et al. Lithium extraction/insertion process on cubic Li-Mn-O precursors with different Li/Mn ratio and morphology[J]. Adsorption, 2011, 17:881-887.
[17] 蒙丽丽, 韦华, 李士霞, 等. 尖晶石型锰酸锂锂离子筛的合成研究[J]. 无机盐工业, 2009, 41(3):37-39.
[18] 许惠, 陈昌国, 宋应华, 等. 锂离子筛前驱体Li₄Mn₅O₁₂的制备及性能[J]. 中国有色金属学报, 2013, 23(10):2868-2874.
[19] Zhang Y C, Wang H, Wang B, et al. Low temperature synthesis of nanocrystalline Li₄Mn₅O₁₂ by a hydrothermal method[J]. Materials Research Bulletin, 2002, 37:1411-1417.
[20] Yang X J, Kanoh H, Tang W P, et al. Synthesis of Li_1.33Mn_1.67O₄spinels with different morphologies and their ion adsorptivities after delithiation[J]. Journal of Materials Chemistry, 2000, 10:1903-1909.
[21] Chitrakar R, Kanoh H, Miyai Y, et al. Recovery of lithium from seawater using manganese oxide adsorbent(H_1.6H_1.6O₄)derived from Li_1.6Mn_1.6O₄[J]. Industrial & Engineering Chemistry Research, 2001, 40:2054-2058.
[22] Shi X C, Zhou D F, Zhang Z B, et al. Synthesis and properties of Li_1.6Mn_1.6O₄ and its adsorption application[J]. Hydrometallurgy, 2011, 110:99-106.
[23] Chitrakar R, Kanoh H, Miyai Y, et al. A new type of manganese oxide(MnO₂·0.5H₂O)derived from Li_1.6Mn_1.6O₄and its lithium ion-sieve properties[J]. Chemistry of Material, 2000, 12:3151-3157.
[24] 王禄, 马伟, 韩梅, 等. 高效锂离子筛吸附剂MnO₂·0.5H₂O的软化学合成及吸附性能研究[J]. 化学学报, 2007, 65(12):1135-1139.
[25] Xiao J L, Sun S Y, Wang J, et al. Synthesis and adsorption properties of Li_1.6Mn_1.6O₄ Spinel[J]. Industrial & Engineering Chemistry Research, 2013, 52(34):11967-11973.
[26] Zhu G R, Wang P, Oi P F, et al. Adsorption and desorption properties of Li⁺ on PVC-H_1.6Mn_1.6O₄ lithium ion-sieve membrane[J]. Chemical Engineering Journal, 2014, 235:340-348.
[27] 孙淑英, 张钦辉, 于建国. 纳米MnO₂离子筛的锂吸附性能[J]. 化工学报, 2007, 58(7):1757-1761.
[28] 陆红岩, 杨立新, 邬赛祥, 等. 三维有序大孔尖晶石型Li_1.6Mn_1.6O₄的制备及锂离子筛吸附特性[J]. 高等学校化学学报, 2011, 32(10):2268-2273.
[29] 毕参参, 李晶, 董殿权. PS微球的制备及三维胶晶模板的组装和应用[J]. 化工新型材料, 2012, 40(5):136-138.
[30] Kim Y S, Kanoh H, Hirotsu T, et al. Chemical bonding of ion-exchange type sites in spinel-type manganese oxides Li_1.33Mn_1.67O₄[J]. Materials Research Bulletin, 2002, 37:391-396.
[31] Feng Q, Kanoh H, Ooi K. Manganese oxide porous crystals[J]. Materials Chemistry, 1998, 9:319-333.
[32] Wang L, Ma W, Liu R, et al. Correlation between Li⁺ adsorption capacity and the preparation conditions of spinel lithium manganese precursor[J]. Solid State Ionics, 2006, 177:1421-1428.
[33] 王盼. 锂离子筛膜的制备及其吸附性能研究[D]. 青岛:中国海洋大学, 2013.
[34] Ammundsen B, Jones D J, Roziere J, et al. Ion exchange in manganese dioxide spinel:Proton, deuteron, and lithium sites determined from neutron powder diffraction data[J]. Chemistry of Materials, 1998, 10:1680-1687.
[35] Ariza M J, Jones D J, Rozieŕe J, et al. Probing the local structure and the role of protons in lithium sorption processes of a new lithium-rich manganese oxide[J]. Chemistry of Materials, 2006, 18:1885-1890.
[36] Darul J, Nowicki W, Piszora P. Unusual compressional behavior of lithium-manganese oxides:A case study of Li₄Mn₅O₁₂[J]. Journal of Physical Chemistry, 2012, 116:17872-17879.
[37] 孙淑英, 张钦辉, 于建国. 低维纳米立方相Li₄Mn₅O₁₂的制备及锂吸附性能[J]. 无机材料学报, 2010, 25(6):626-630.
[38] 竺柏康, 王东光, 任益枰, 等. 新型磁性纳米锂离子筛的合成[J]. 化工学报, 2011, 62(7):2067-2074.
[39] 闫树旺, 钟辉, 黄志华. 粒状二氧化钛交换剂的研制及从卤水中提取锂[J]. 离子交换与吸附, 1994, 10(3):219-225.
[40] 李超, 肖伽励, 孙淑英, 等. 球形离子筛吸附剂的制备及其锂吸附性能评价[J]. 化工学报, 2014, 65(1):220-226.
[41] 孟兴智. 离子筛型锂吸附剂的成型及其性能研究[D]. 天津:河北工业大学, 2005.
[42] Hong H J, Park I S, Ryu T, et al. Granulation of Li_1.33Mn_1.67O₄(LMO)through the use of cross-linked chitosan for the effective recovery of Li⁺ from seawater[J]. Chemical Engineering Journal, 2013, 234:16-22.
[43] Xiao G P, Tong K F, Zhou L S, et al. Adsorption and desorption behavior of lithium ion in spherical PVC-MnO₂ ion sieve[J].
Industrial & Engineering Chemistry Research, 2012, 51:10921-10929.
[44] 邱实. 基于碳纳米管的有机/无机杂化膜的制备及性能研究[D]. 杭州:浙江大学, 2011.
[45] Umeno A, Miyai Y, Takagi N, et al. Preparation and adsorptive properties of membrane-type adsorbents for lithium recovery from seawater[J]. Industrial & Engineering Chemistry Research, 2002, 41(17):4281-4287.
[46] Chung K S, Lee J C, Kim W K, et al. Inorganic adsorbent containing polymeric membrane reservoir for the recovery of lithium from seawater[J]. Journal of Membrane Science, 2008, 325:503-508.
[47] 解利昕, 陈小棉. Li_1.6Mn_1.6O₄/PVDF多孔膜的制备及提锂性能[J]. 化工学报, 2014, 65(1):237-243.
[48] Yang S S, Liu X, Shen J N, et al. Applied Mechanics and Materials[M]. Switzerland:Trans Tech Publications, 2014.
[49] 赵丽丽, 王榕树. 锂离子交换剂制备及交换反应动力学[J]. 物理化学学报, 2003, 19(10):933-937.
[50] Yuan J S, Yin H B, Ji Z Y, et al. Effective recycling performance of Li⁺ extraction from spinel-type LiMn₂O₄with persulfate[J]. Industrial & Engineering Chemistry Research, 2014, 53:9889-9896