Effects of conductive agent type on lithium extraction from salt lake brine with LiFePO_(4) electrodes

Electrochemical lithium extraction from salt lakes is an effective strategy for obtaining lithium at a low cost.Nevertheless,the elevated Mg:Li ratio and the presence of numerous coexisting ions in salt lake brines give rise to challenges,such as prolonged lithium extraction periods,diminished lithium extraction efficiency,and considerable environmental pollution.In this work,Li FePO4(LFP)served as the electrode material for electrochemical lithium extraction.The conductive network in the LFP electrode was optimized by adjusting the type of conductive agent.This approach resulted in high lithium extraction efficiency and extended cycle life.When the single conductive agent of acetylene black(AB)or multiwalled carbon nanotubes(MWCNTs)was replaced with the mixed conductive agent of AB/MWCNTs,the average diffusion coefficient of Li+in the electrode increased from 2.35×10^(-9)or 1.77×10^(-9)to 4.21×10^(-9)cm^(2)·s^(-1).At the current density of 20 mA·g^(-1),the average lithium extraction capacity per gram of LFP electrode increased from 30.36 mg with the single conductive agent(AB)to 35.62 mg with the mixed conductive agent(AB/MWCNTs).When the mixed conductive agent was used,the capacity retention of the electrode after 30 cycles reached 82.9%,which was considerably higher than the capacity retention of 65.8%obtained when the single AB was utilized.Meanwhile,the electrode with mixed conductive agent of AB/MWCNTs provided good cycling performance.When the conductive agent content decreased or the loading capacity increased,the electrode containing the mixed conductive agent continued to show excellent electrochemical performance.Furthermore,a self-designed,highly efficient,continuous lithium extraction device was constructed.The electrode utilizing the AB/MWCNT mixed conductive agent maintained excellent adsorption capacity and cycling performance in this device.This work provides a new perspective for the electrochemical extraction of lithium using LFP electrodes.

Extraction of lithium from salt lake brine by aluminum-based alloys

Salt lake brine was reacted with activated aluminum-based alloys and lithium was precipitated.The effects of aluminum-based alloys on precipitating lithium were investigated and the reasonable alloy used to extract lithium from brine was obtained.The effects of the mole ratio of Al to Li and Ca content of Al-Ca alloy,the initial concentration of lithiumion ion in solution,reaction temperature and reaction time on the adsorption rate of lithium were studied,and the optimized process parameters were determined.The results show that the mole ratio of Al to Li and Ca content of Al-Ca alloy and reaction temperature have great influences on the precipitation rate of lithium.The precipitation rate of lithium reaches 94.6% under the optimal condition,indicating that Al-Ca alloy is suitable for the extraction of lithium from salt lake brine.

Highly efficient extraction of lithium from salt lake brine by LiAl-layered double hydroxides as lithium-ion-selective capturing material

The extraction of lithium from salt lake brine in the Chinese Qaidam Basin is challenging due to its high Mg/Li and Na/Li ratios. Herein, we utilized a reaction-coupled separation technology to separate sodium and lithium ions from a high Na/Li ratio brine(Na/Li = 48.7, w/w) and extracted lithium with Li Al-layered double hydroxides(Li Al-LDHs). The Li Al-LDHs act as lithium-ion-selective capturing materials from multication brines. That is, the lithium ions selectively enter the solid phase to form Li Al-LDHs, and the sodium ions are still retained in the liquid phase. This is because the lithium ions can be incorporated into the structural vacancies of LiAl-LDHs, whereas the sodium ions cannot. The effects of reaction conditions on lithium loss and separation efficiency were investigated at both the nucleation and the crystallization stage, e.g., the nucleation rotating speed, the Li/Al molar ratio, the crystallization temperature and time, and co-existing cations. The lithium loss is as low as 3.93% under optimal separation conditions.The sodium ions remained in the solution. Consequently, an excellent Na/Li separation efficiency was achieved by this reaction-coupled separation technology. These findings confirm that LiAl-LDHs play a critical function in selectively capturing lithium ions from brines with a high Na/Li ratio, which is useful for the extraction of lithium ions from the abundant salt lake brine resources in China.

Lithium Ion Extraction from the High Ration Mg/Li Salt Lake Brine with Ionic Liquid in Triisobutyl Phosphate and Kerosene

1 Introduction As the lightest metal with the unique properties of energy production and storage,lithium is regarded as the new century energy metal.Lithium and its compounds were widely used in various industrial fields,especially in

The Phase Diagram of Lithium Salt Systems and Its Application in Extraction of Lithium from Salt Lake Brine

At present,the extraction of lithium from salt lake brine is the new trend of the salt lake industrialization.The saltine lake lithium resources are extremely rich in western china,especially in Qinghai-Tibetan plateau.Brine of salt

Doping engineering of lithium-aluminum layered double hydroxides for high-efficiency lithium extraction from salt lake brines

Lithium-aluminum layered double hydroxides(LiAl-LDH)have been be successfully applied in commercial-scale for lithium extraction from salt lake brine,however,further advancement of their applications is hampered by suboptimal Li^(+)adsorption performance and ambiguous extraction process.Herein,a doping engineering strategy was developed to fabricate novel Zn^(2+)-doped LiAl-LDH(LiZnAl-LDH)with remarkable higher Li^(+)adsorption capacity(13.4 mg/g)and selectivity(separation factors of 213,834,171 for Li^(+)/K^(+),Li^(+)/Na^(+),Li^(+)/Mg^(2+),respectively),as well as lossless reusability in Luobupo brine compared to the pristine LiAl-LDH.Further,combining experiments and simulation calculations,it was revealed that the specific surface area,hydrophilic,and surface attraction for Li^(+)of LiZnAl-LDH were significantly improved,reducing the adsorption energy(Ead)and Gibbs free energy(ΔG),thus facilitating the transfer of Li^(+)from brine into interface followed by insertion into voids.Importantly,the intrinsic oxygen vacancies derived from Zn-doping depressed the diffusion energy barrier of Li^(+),which accelerated the diffusion process of Li^(+)in the internal bulk of LiZnAl-LDH.This work provides a general strategy to overcome the existing limitations of Li^(+)recovery and deepens the understanding of Li^(+)extraction on LiAl-LDH.

Problems of Lithium Isotope Research in Salt Lake Study

Lithium in nature mainly exists in the forms of solid minerals and ionic liquid.More than 150 lithium minerals exist,which are mainly pegmatite mineral including triphane,lithionite and petalite.Liquid lithium mainly

Natural Evaporation of Dangxiongcuo Salt Lake Spring Brine in Tibet,China

1 Introduction Dangxiongcuo salt lake(Figure 1),which is located in the southwest of Tibet,China,is rich in valuable mineral elements like lithium,potassium,boron,rubidium,caesium

Classification and mineralization of global lithium deposits and lithium extraction technologies for exogenetic lithium deposits

A reasonable classification of deposits holds great significance for identifying prospecting targets and deploying exploration. The world ’s keen demand for lithium resources has expedited the discovery of numerous novel lithium resources. Given the presence of varied classification criteria for lithium resources presently, this study further ascertained and classified the lithium resources according to their occurrence modes, obtaining 10 types and 5 subtypes of lithium deposits(resources) based on endogenetic and exogenetic factors. As indicated by surveys of Cenozoic exogenetic lithium deposits in China and abroad,the formation and distribution of the deposits are primarily determined by plate collision zones, their primary material sources are linked to the anatectic magmas in the deep oceanic crust, and they were formed primarily during the Miocene and Late Paleogene. The researchers ascertained that these deposits,especially those of the salt lake, geothermal, and volcanic deposit types, are formed by unique slightly acidic magmas, tend to migrate and accumulate toward low-lying areas, and display supernormal enrichment. However, the material sources of lithium deposits(resources) of the Neopaleozoic clay subtype and the deep brine type are yet to be further identified. Given the various types and complex origins of lithium deposits(resources), which were formed due to the interactions of multiple spheres, it is recommended that the mineralization of exogenetic lithium deposits(resources) be investigated by integrating tectono-geochemistry, paleoatmospheric circulation, and salinology. So far, industrialized lithium extraction is primarily achieved in lithium deposits of the salt lake, clay, and hard rock types. The lithium extraction employs different processes, with lithium extraction from salt lake-type lithium deposits proving the most energy-saving and cost-effective.

Study of Lithium Exploitation from Tibetan Kyetsé Tsakha and Lungmu Tso Salines by Freezing and Mixing

1 Introduction Lithium was used widely in batteries,lubricants,aluminium smelting,ceramics,glass,polymers and other areas due to its unique electrochemical reactivity as well as other properties(Hykawy,2010).Production of lithium comes from both brine and mineral sources.The total resources of lithium estimated by the USGS in 2014 are to

溶析结晶用于盐湖卤水提钾和镁锂分离研究

采用溶析结晶法快速分离盐湖卤水中氯化钾并降低卤水中的镁锂比,解决青海盐湖盐田摊晒存在的生产周期长、需要修建大面积盐田等难题。以有机溶剂为溶析剂,考察了不同种类溶析剂加入量、溶析温度、溶析时间等对盐湖氯化钾收率及镁锂比的影响。实验结果表明,以无水乙醇为溶析剂与盐湖卤水体积比为2∶1,溶析温度为-15℃,时间为90 min时,氯化钾和氯化钠的收率分别达到93.15%和99.84%。溶析结晶后的母液经过过滤,在70~80℃,以0.5℃/min的降温速率进行动态降温,析出氯化镁晶体,镁锂质量比由原卤中的388.44降低至266.63,最终达到快速分离氯化钾的目的及为后续对镁锂进一步分离提供更有利的条件。

造粒的氮掺杂碳纳米管基吸附剂对卤水中硼的吸附行为与机理

盐湖卤水中硼资源丰富,存在形式复杂多样,分离和回收硼的意义重大。基于N掺杂强静电与多羟基协同作用能够有效提高硼阴离子的分离机制,设计以水合肼为N源,多羟基的一维纳米材料碳纳米管(CNTs)为多羟基络合基,采用简单的一锅水热法合成了N掺杂的碳纳米管硼吸附材料(N-CNTs)。此外,以改性的聚丙烯腈为造粒剂,经造粒后,最大硼吸附容量为20.45 mg/g,特别在低浓度硼的分离中表现出优异的性能,这使N-CNTs成为硼的高效吸附材料。吸附机理为一维碳纳米管和改性聚丙烯腈的高比表面积上多羟基与N掺杂位置发生强静电协同增强络合吸附。硼吸附过程符合朗格缪尔吸附等温模型和准二阶动力学模型,在高浓盐多离子溶液中表现出优异的选择性硼吸附性能。该吸附剂在东台吉乃尔盐湖卤水中硼的吸附容量达18.92±1 mg/g,该技术在盐湖卤水及水处理行业具有较高的应用潜力。

Extraction of Lithium from Salt Lake Brine with Triisobutyl Phosphate in Ionic Liquid and Kerosene

Three ionic liquids（ILs）, namely, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-me- thylimidazolium bis[（trifluoromethyl）sulfonyl]imide and 1-ethyl-3-methylimidazolium bis[（trifluoromethyl）sul- fonyl]imide with the triisobutyl phosphate（TIBP） and kerosene system were respectively used to extract lithium ion from salt lake brine with a high concentration ratio of magnesium and lithium experimentally. Results indicate that the highest extraction selectivity for lithium was obtained with IL 1-ethyl-3-methylimidazolium bis[（trifluoromethyl）- sulfonyl]imide. The effects of solution pH and phase ratio R（O/A） on the extractive step and the influence of acid concentration of the stripping solution and R（O/A） on the back extraction step were also investigated systematically. The single-step extraction efficiency of lithium ion was 83.71% under the optimal extraction conditions, and the single-step back extraction efficiency was 85.61% with a 1.0 mol/L HCI in 1.0 mol/L NaCI medium as stripping agent at R（O/A）=2. The liquid-liquid extraction mechanism and the complex of the ligand with lithium were proposed.

富锂硫酸盐型盐湖卤水蒸发实验研究进展

随着“双碳”目标的提出,锂在新能源材料领域中的应用受到高度关注,锂的需求呈现爆发式增长。世界锂资源以矿石锂和盐湖锂为主,盐湖锂因其储量大成为未来锂资源开发的重点,因而占比最大的硫酸盐型盐湖成为焦点。因盐湖卤水组成差异较大,叠加硫酸盐型盐湖特殊属性,使得锂在盐田蒸发阶段存在多种结晶形式而造成损失,增加了锂的有效富集难度。总结了前人针对富锂硫酸盐型盐湖的蒸发实验研究结果,结合相图分析总结富锂硫酸盐型盐湖蒸发结晶析盐规律,重点关注锂的浓缩状态及析盐结晶形式,为硫酸盐型盐湖锂资源开发提供参考。

锂资源提取技术研究进展

锂被认为是21世纪最重要的能源金属之一,在全球减碳的共同目标下,新能源产业快速发展,推动过去3a锂消费量的持续增长,引发国内外对提锂技术的研究热潮。根据锂资源的赋存状态,对矿石提锂及卤水提锂技术进行综述,系统性地总结对比了各种方法的优缺点。从矿石中提取锂的方法主要有石灰石烧结法、硫酸法、硫酸盐法、压煮法、氯化焙烧法、直接酸浸法;卤水提锂中受到广泛关注的技术主要有沉淀法、吸附法、溶剂萃取法、膜分离法、电化学法。由于碳酸锂价格高位回落,国际锂盐获取形势愈加严峻,因此不断开发并完善提锂技术,增强中国的锂资源自供自给能力,实现提锂技术的降本增效势在必行。

国内外提锂技术研究进展及应用

随着双碳政策的实施,新能源汽车产业快速发展,高容量的锂电池得到了大规模的应用,因此,绿色、高效的提锂技术成为决定最终锂资源回收经济效益的关键因素。根据资源类型的差异,提锂技术可分为盐湖卤水提锂和矿石提锂技术两种。盐湖卤水主要用于生产工业级的碳酸锂,工艺流程简单,成本较低,但其生产条件较差,常伴随较高的Mg/Li。盐湖卤水提锂技术主要分为分步沉淀法和吸附法两种,分别用来处理低、高Mg/Li盐湖卤水资源。锂辉石、锂云母、锂黏土等锂矿石主要用于生产电池级碳酸锂,提锂工艺成熟,但生产成本高,环境污染较为严重,目前常用的工艺为硫酸焙烧法、硫酸盐培烧法、氯化焙烧法、石灰石焙烧法和碱性压煮法。结合盐湖卤水、锂辉石、锂云母和锂黏土等目前主要的锂资源,从资源储量分布、典型工艺流程、代表性矿山项目以及相应的运营成本分析等方面详细阐述了国内外锂资源提锂技术的研究和应用现状,并通过对不同锂矿资源开发技术在应用过程中的优缺点对比分析,从工业应用价值的角度来阐述现有技术中制约提锂效率的关键因素,并据此提出了不同锂资源提锂技术未来的发展方向,为提锂技术的优化更新提供相应的参考。

盐湖卤水萃取法提锂的研究进展

随着全球锂电行业的迅猛发展,作为原材料的锂需求量也日益攀升。盐湖卤水中蕴含着丰富的锂资源,但浓度低、成分复杂。开发高效锂分离技术,从卤水中提取锂资源具有重要的经济价值和战略意义。溶剂萃取法具有处理量大、萃取效率高、优异选择性以及易于规模化操作等优点,具有良好的工业应用前景。本文主要综述了近5年常用的萃取体系,包括β-二酮、有机磷化合物、大环分子、磷酰基吡唑啉酮、离子液体以及低共熔溶剂。系统地分析了各种萃取体系的作用机理、适用的环境以及存在的优缺点,对于萃取体系存在的问题进一步介绍了萃取过程强化技术,如膜萃取强化、电场强化。最后,对未来各种萃取体系的研究重点和改进提出了观点和评述,同时对萃取体系的发展前景进行了展望。

吸附—膜耦合法从高镁锂比盐湖卤水中提锂

中国的锂资源主要赋存于高镁锂比盐湖卤水中,提锂难度较高,单一分离手段难以高效提锂,多种盐湖提锂技术的耦合是盐湖提锂的未来发展趋势。采用吸附—膜耦合法对盐湖卤水进行处理,在优化条件下实现了高选择性锂吸附,动态脱附后卤水镁锂比从105.2降低至1.49。考察了不同条件对纳滤膜分离纯化锂的影响。纳滤膜在稀释倍数1.0、温度20℃、操作压力0.4 MPa、pH 4.66、产水原料液比0.54的条件下,锂截留率为2.63%、分离因子为27.3、渗透通量为7.125 L/(m^(2)·h),最终产水镁锂比从最初的105.2降低至0.05,实现了对高镁锂比盐湖卤水中锂资源的绿色高效提取。

锂离子筛在盐湖卤水提锂中的研究进展

综述了锰基锂离子筛、钛基锂离子筛、铝基吸附剂中Li+的脱出、嵌入机理,重点介绍了LIS制备及改性的研究现状和进展,分析了LIS在含Li+溶液中的提锂机理及影响吸附效果的因素;总结了锂离子筛材料中存在的一些问题,并对锂离子筛未来的研究重点和发展方向进行了展望。

察尔汗盐湖老卤锂富集多级精控盐田工艺扩大实验

这是一篇矿业工程领域的论文。针对察尔汗盐湖老卤中锂离子的浓缩富集,采用蒸发结晶、分步分离的方法完成了老卤锂富集多级精控盐田工艺扩大实验,研究了锂、硼在蒸发过程中的富集规律,使锂离子浓度达到1 g/L以上,并获得了高品质的水氯镁石。对盐田蒸发过程进行了物料衡算,得到了各析盐阶段的实际成卤量和锂收率,以及日晒盐田的生产能力和各级盐田面积分配比例等,能够为今后实现察尔汗盐湖提钾老卤的综合开发利用提供可靠的数据支持。