纳滤法用于铝锂分离的初步研究

本文探讨了纳滤分离Al³⁺和Li⁺的可行性,研究了含盐量和铝锂比对分离效率的影响,提出了从锂云母浸出液中分离回收锂的新方法。实验结果表明,纳滤膜对Al³⁺和Li⁺的截留率随含盐量的升高而降低,其中Li⁺始终呈现负浓度梯度扩散的趋势,而Al³⁺的截留率始终稳定在99%以上。当含盐量为45 g/L时,铝锂分离因子最高可达248.33,膜面相应Zeta电位的绝对值达到最大。随着溶液中铝锂比的变化,Al³⁺和Li⁺的截留率分别在不同铝锂比的条件下出现拐点,溶液的pH呈现先下降后上升最后下降的复杂趋势。本实验研究发现,DK膜能够在酸性环境下实现高效的铝锂分离和锂的浓缩,从而为锂云母浸出液中锂的提取提供新的思路。     

Towards a Li barometer for bimineralic eclogites: experiments in CMAS

An eclogite barometer has profound importance in the study of upper mantle processes and potential application to diamond prospecting. Studies on the partitioning of Li between clinopyroxene (cpx) and garnet (grt) in natural samples have shown that this particular element is very sensitive to changes in pressure and could be calibrated as the barometer demanded for bimineralic eclogites. Experiments were performed from 4 to 13 GPa and 1,100–1,400°C in the CMAS (CaO, MgO, Al₂O₃, SiO₂) system with Li added as Li₃PO₄ to quantify this pressure dependence into a barometer expressed in the following equation: P = (0.00255T – ln K _d)/0.2351 where P is in GPa, T is in °C and K _d is defined as the partition coefficient of Li (in ppm) between clinopyroxene and garnet. The experimental pressures are reproduced to ±0.38 GPa (1σ) by this equation. This barometer is strictly applicable only to CMAS. Experiments at 1,300°C, 8–12 GPa showed that Henry’s Law is fulfilled for Li partitioning between cpx and grt in the concentration range of approximately 0.01–1 wt% Li. Direct application of the equation to experiments in natural systems performed at 1,300°C from 4 to 13 GPa consistently overestimates pressures by approximately 2 GPa. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

http://www.sciencedirect.com/science/article/pii/S1674987110000149

The structural stability of manganese titanate MnTiO3 at high pressure was investigated by X-ray diffraction and Raman spectroscopy with diamond anvil cells. Ilmenite-type MnTiO3 is stable at least to 26.6 GPa, and lithium niobate type MnTiO3 reversibly transforms at room temperature to perovskite at 2.0 GPa. Bulk moduli (K300) of ilmenite, lithium niobate and perovskite are 174(4) GPa, 179(8) GPa, and 208(5) GPa, respectively (at fixed first pressure derivative K′ = 4). The Grüneisen parameter γ has been estimated to be 1.28 for ilmenite and 1.75 for perovskite. In ilmenite phase, TiO6 octahedra become more regular with increasing pressure. In perovskite phase structural distortion increases with pressure increase.     

Lithium isotopes in foraminifera shells as a novel proxy for the ocean dissolved inorganic carbon (DIC)

Past ocean pH and pCO₂ are critical parameters for establishing relationships between Earth's climate and the carbon cycle. Previous pCO₂ estimates are associated with large uncertainties and are debated. In this study, laboratory cultures of the foraminiferan genus Amphistegina were performed in order to examine the possible factors that control the Li isotope composition (δ⁷Li) of their shells. δ⁷Li is insensitive to temperature and pH variations but correlates positively with the Dissolved Inorganic Carbon (DIC) of seawater. Li/Ca ratio in the shells shows negative correlation with δ⁷Li, consistent with published data for planktonic foraminifera from core tops and from short periods during the Cenozoic. We propose that the sensitivity of δ⁷Li and Li/Ca ratio to DIC is a biological phenomenon and is related to biomineralization mechanisms in foraminifera. We used the published foraminiferal δ⁷Li records, and our experimental results, to determine the paleo-ocean DIC and pH for the last glacial–interglacial cycle. The results are consistent with published estimates of pH and pCO₂ based on boron isotopes and ice cores. We suggest Li and its isotopes may serve as a new complementary proxy for the paleo-ocean carbonate chemistry.     

锂矿主要类型、特征、时空分布及找矿潜力分析

锂是重要的能源金属,分布高度集中。目前可开发利用的锂矿床主要有盐湖卤水型、伟晶岩型、黏土型、锂沸石型、其他卤水型（包括油气田卤水亚类和地热卤水亚类）和离子吸附型6种类型。除伟晶岩型锂矿的时代呈幕式分布,其他类型的锂矿主要集中形成于新生代。新生代锂矿占全球已查明资源量的75%,主要分布于显生宙造山带如安第斯锂三角地区、中国川藏地区、北美科迪勒拉等地区,其余锂矿则主要分布在前寒武纪克拉通如西澳克拉通、刚果克拉通、西非克拉通和加拿大地盾等区域。盐湖卤水型和伟晶岩型锂矿找矿潜力大,是目前勘探开发的主要类型。

     

中国盐湖资源的开发利用与科技问题

我国青海、西藏、新疆、内蒙古等西部地区盐湖分布广泛,盐湖中蕴藏着丰富的钾、镁、锂、硼等盐类资源,潜在经济价值极大。开发利用这些资源对于西部地区经济发展、社会稳定和满足国家对钾、锂、镁、硼等的需求具有重要的现实意义。要认真考虑西部地区自然生态条件的脆弱性,一定要本着可持续发展原则搞好盐湖资源开发。在发展盐湖钾肥工业的同时,要高度重视和解决共生资源的综合利用。
介绍了我国盐湖资源现状,分析了国民经济发展对盐湖资源的需求情况,讨论了制约盐湖资源开发利用的重大科技问题。在介绍国内外盐湖科技发展现状与趋势的基础上,提出了盐湖资源综合利用的基本思路、科技发展目标,以及技术示范基地建设、支撑条件等方面的建议与政策措施。指出现阶段盐湖资源开发利用的主要力量应放在占我国总钾资源97%的柴达木盆地,通过加强盐湖资源开发科技攻关和加快产业化进程,解决制约盐湖钾、锂、镁、硼等资源的综合利用问题,加快盐湖资源综合利用工程示范基地的建设,在此基础上建设综合利用钾、锂、镁、硼等资源的现代化企业,为可持续开发西部资源做贡献。     

Insights into Li and Li isotope cycling and sub-arc metasomatism from veined mantle xenoliths,Kamchatka

Harzburgitic xenoliths cut by pyroxenite veins from Avachinsky volcano, Kamchatka, are derived from the sub-arc mantle and record element transfer from the slab to the arc. Olivine and orthopyroxene in the harzburgites have Li isotopic compositions (δ⁷Li = +2.8 to +5.6) comparable to estimates of the upper mantle (δ⁷Li ~ +4 ± 2). The pyroxenite veins, which represent modal metasomatism and may therefore provide information about the metasomatic agent, have mantle-normalized trace element characteristics that suggest overprinting of their mantle source by an aqueous, slab-derived fluid. These include relative enrichments of Pb over Ce, U over Th and Sr over Nd. Li is enriched relative to the HREE, and ortho- and clinopyroxene from the veins are in Li elemental and isotopic equilibrium with each other and the surrounding harzburgite. Vein samples (δ⁷Li = +3.0 to +5.0) do not record a significant slab-derived δ⁷Li signature. These observations can be reconciled if slab Li diffusively re-equilibrates in the mantle wedge. Modeling demonstrates that Li equilibration of small (1–2 cm width) veins or melt conduits is achieved at mantle wedge temperatures within 10¹–10⁵ years. We conclude that strongly fractionated Li isotopic signatures cannot be sustained for long periods in the sub-arc mantle, at least at shallow (<70 km) depths. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

伟晶岩型锂矿床研究现状及其在中国西部的找矿前景

锂现为全球战略性关键金属矿产,花岗伟晶岩型锂矿是锂资源的重要类型之一,也是当前国际矿床学的研究热点。花岗伟晶岩划分为LCT（Li–Cs–Ta）、NYF（Nb–Y–F）及二者混合的LCT+NYF型,其中LCT型伟晶岩富集稀有元素Li、Rb、Cs、Be、Ga、Sn、Ta、Nb及B、P、F等助熔剂,通常与伸展背景下的晚造山和造山后阶段过铝质S型花岗岩具有成因联系。笔者分析了全球伟晶岩型锂矿床的时空分布特征,发现锂矿成矿事件主要发生在超大陆会聚造山作用的中晚期。研究表明中国花岗伟晶岩型锂矿空间分布相对集中,主要分布在9个锂成矿带,成矿期以三叠纪为主。花岗质岩浆结晶分异和下地壳物质低程度的部分熔融是伟晶岩两种主要的形成方式。稀有金属伟晶岩的成矿机制主要有分离结晶作用、岩浆不混溶、超临界流体和组成带状纯化。总结分析了中国西部西昆仑、川西松潘–甘孜、阿尔泰等3个典型伟晶岩型锂矿带的的成矿特点、分布特征、研究进展及找矿前景,并提出了构造–岩浆–变质–成矿的耦合关系是制约锂成矿过程和富集规律的关键科学问题。     

锂离子二次电池及其电解质的研究

介绍了锂离子二次电池的发展以及与其它二次电池性能的比较,并对影响锂离子二次电池性能的几个问题作了阐述。着重论述了锂离子二次电池的电解质及其导电性能,以及制备六氟磷酸锂的方法。     

库仑法和电化学阻抗法测量LiFePO4锂离子扩散系数

库仑法和电化学阻抗法是测量锂离子扩散系数有效的测量手段。以实验室自制的LiFePO4为实验电池正极材料,介绍如何用库仑法和阻抗法测试并计算电极材料的锂离子扩散系数。库仑法计算得到锂离子扩散系数由Li1-xFePO4(x=0)的9.6×10-9cm2.s-1变化为Li1-xFePO4(x=0.7)的1.1×10-11cm2.s-1。用阻抗法的两种模型,分别计算了Li1-xFePO4(x=0.65)的电池材料的锂离子扩散系数,结果分别是8.5×10-11cm2.s-1和3.1×10-12cm2.s-1。三种方法的计算结果接近。