Highly Selective Lithium Ion Adsorbents:Polymeric Porous Microsphere with Crown Ether Groups

In this study, we prepared and applied polymeric porous microsphere adsorbents with selectivity for Li^+ extraction from aqueous solution. We synthesized the adsorbents by suspension polymerization using methacryloyoxyme-12-crown-4(M12C4) as a functional monomer, which had been synthesized from 2-hyroxymethyl-12-crown-4 and methacryloyl chloride. We verified the chemical composition by solid nuclear magnetic resonance(13C-NMR) spectroscopy and observed the porous structure by scanning electron microscopy(SEM). We conducted adsorption isothermal and kinetic tests to determine the adsorption properties. It was found that the adsorbents showed high adsorption efficiency and an adsorption equilibrium time of 200 min. In addition, since the crown ether used in this work could form a stable complex with Li^+, we observed good selectivity for Li^+ in the prepared solution compared with other ions such as Na^+, K^+, Mg^(2+), and Ca^(2+). We reused the adsorbents five times with no significant decrease in adsorptive capacity.

Application of diatomite as an effective polysulfides adsorbent for lithium-sulfur batteries

The lithium–sulfur batteries show the great potential to be the most promising candidate for high energy applications. However, the shuttling of soluble polysulfides deteriorates the battery performance tremendously. To suppress the diffusion of soluble polysulfides, diatomite that has abundant natural three-dimensional ordered pores is incorporated into the cathode to trap polysulfides. The composite cathode material(S-DM-AB for short), including sulfur(S), diatomite(DM), and acetylene black(AB) is prepared by an impregnation method. For comparison, another composite cathode material(S-AB for short) including sulfur and acetylene black is also prepared by the same method. The battery with S-DMAB composite cathode material delivers a discharge capacity of 531.4 m Ah/g after 300 cycles at 2 C with a capacity retention of 51.6% at room temperature. By contrast, the battery with S-AB composite cathode material delivered a capacity of only 196.9 m Ah/g with a much lower capacity retention of 18.6% under the same condition. The addition of diatomite in the cathode is proved to be a cheap and effective way to improve the life time of the lithium sulfur batteries.

Novel Nanosized Adsorbing Composite Cathode Materials for the Next Generational Lithium Battery

A novel carbon-sulfur nano-composite material was synthesized by heating sublimed sulfur and high surface area activated carbon （HSAAC） under certain conditions. The physical and chemical per- formances of the novel carbon-sulfur nano-composite were characterized by scanning electron microscopy （SEM）, Brunauer-Emmett-Teller （BET） and X-ray diffraction （XRD）. The electrochemical performances of nano-composite were characterized by charge-discharge characteristic, cyclic voltammetry and electrochemical impendence spectroscopy （EIS）. The experimental results indicate that the electrochemical capability of nano- composite material was superior to that of traditional S-containing composite material. The cathode made by carbon-sulfur nano-composite material shows a good cycle ability and a high specific charge-discharge capacity. The HSAAC shows a vital role in adsorbing sublimed sulfur and the polysulfides within the cathode and is an excellent electric conductor for a sulfur cathode and prevents the shuttle behavior of the lithium-sulfur battery.

锂铝层状双金属氢氧化物的制备及其锂脱嵌过程

锂铝层状双金属氢氧化物(Li/Al-LDHs)是一种适用于高镁锂比卤水中提锂的吸附剂,但其存在吸附容量偏低、吸附机理与适用条件不够清晰等问题。本工作以铝粉、氢氧化锂为原料制备Li/Al-LDHs,考察了适用条件下溶液中阴阳离子对吸附过程的影响并进行了不同溶液组成下的提锂性能测试,结合红外光谱测试和X射线光电子能谱等表征明晰了锂脱嵌机理。结果表明,Li/Al-LDHs在卤水中的最大吸附容量为8.350mg/g,阳离子选择性顺序为Li^(+)>Na^(+)>Mg^(2+)>Ca^(2+)>K^(+)。Li/Al-LDHs对Li^(+)的吸附符合Langmuir等温吸附模型和准二级吸附动力学模型,吸附过程主要是基于尺寸筛分效应进行的,Li^(+)进入吸附剂层间的空位后需要等量的阴离子(Cl^(-)、SO_(4)^(2-)等)进行电荷平衡,其吸锂容量随溶液体系总离子浓度的增加而变大,因此更适用于从高含盐量卤水中提锂。研究结果可为后续废旧金属铝制取Li/Al-LDHs用于盐湖卤水提锂提供技术参考。

油气田水伴生资源提取技术进展及应用

近年来,随着油气勘探力度的逐渐增大,油气田水量逐年增加,由此带来诸多环境问题,而部分油气田水中的伴生元素的含量均超过工业开采品位,适合综合开采或者单独开采。因此,分析油气田水中伴生元素综合利用的可行性并提出可行技术路线具有重要意义。对油气田水的水质特点和资源分布特征进行了总结,剖析了油气田水中伴生元素锂、溴、钾提取技术的研究和应用现状,阐述了目前盐湖卤水中锂、溴、钾提取技术对于油气田水的适用性及其存在的问题。结合油气田水中伴生元素提取技术和应用现状,认为吸附法提锂+热溶冷结晶法(或冷分解−浮选工艺)提钾+电氧化法提溴是油气田水中伴生有价元素综合利用可行的技术路线。目前的油气田水产业化只针对提锂,应尽快打通伴生资源综合利用全流程,寻求环保经济的油气田水伴生资源综合利用和达标处理工艺,为进一步工业化应用提供理论支撑,助力油气行业绿色高质量发展。

钛基锂离子筛纳米材料研究进展

随着以锂离子电池为代表的新能源行业的兴起,锂需求量大幅增加,因此盐湖卤水提锂技术受到广泛关注。以锂离子筛作为吸附剂的盐湖卤水提锂技术具有环保、高效以及可持续发展的特点。介绍了盐湖卤水提锂技术的类型,综述了钛基锂离子筛的合成方法及钛基锂离子筛纳米材料的研究进展,并对比了不同钛基锂离子筛合成方法的优缺点,最后对钛基锂离子筛的研究方向进行了展望。

锂吸附剂在油气田卤水中的性能评价

目的油气田卤水含有石油类、悬浮物等杂质,对锂资源的吸附分离存在潜在影响,考查了气田水吸附提锂的可行性及市面主流吸附剂的吸附提锂适应性。方法研究对比了pH、温度对铝系、钛系和锰系3种粉体吸附剂吸附、解吸效果的影响规律;对优选的铝系吸附剂,研究了其吸附剂形态、进卤量、进卤流量对成型吸附剂吸附、解吸效果的影响规律,并评估其循环稳定性。结果在最优条件下,3种粉体吸附剂饱和吸附容量分别约为7.9 mg/g、12.5 mg/g、15.3 mg/g。铝系吸附剂解吸液中钠锂比、钾锂比等要优于钛系和锰系,并且钛系和锰系吸附剂溶损率分别是铝系的20倍和70倍,长期运行情况下使用寿命要远低于铝系吸附剂。采用陶瓷膜去除卤水中的悬浮物和石油类,铝系成型吸附剂在进卤量为20 BV(1 BV=50 mL)、进卤流量为12 BV/h、解吸水量为10 BV、解吸流量为10 BV/h的条件下,连续10次循环单柱实验铝系吸附剂吸附容量和尾卤锂浓度保持稳定,平均锂吸附率为79.2%。结论综合证实采用吸附法提取龙王庙气田卤水中的锂资源是可行。

铁掺杂铝基锂吸附剂的制备及其在地下卤水提锂应用研究

为了提高地下盐卤中锂资源利用率,文章采用共沉淀法制备了铁掺杂改性的锂—铝层状双氢氧化物(Li-Fe-Al LDH),并通过选择醋酸纤维素粘结剂和碳酸氢钠致孔剂对改性吸附剂粉末造粒,成功制备了高比表面积的Li-Fe-Al LDH颗粒(GLDH)。结构表征结果表明:所制备的吸附剂粉末具有高纯度LDH晶体结构,而在致孔剂作用下获得颗粒化的GLDH的比表面积为44.449 m^(2)/g,内部平均孔径归为介孔(~18.34 nm),这有助于Li^(+)在吸附剂颗粒内快速扩散。然后,采用地下卤水进行吸附工艺探究,研究结果表明:在相同固液比条件下,随着温度的升高,吸附容量逐渐增加;在相同温度下,随着固液比的增加,吸附容量也逐渐增加,且在提锂过程中吸附动力学更符合伪二级动力学模型,表明卤水中Li^(+)在LDH中吸附遵循化学吸附过程。

盐湖铝系提锂吸附剂成型条件的影响研究

旨在深入研究盐湖铝系提锂吸附剂的成型条件对其性能的影响,并通过系统的试验设计和数据分析,致力于优化提锂吸附剂的制备工艺,以提高其吸附性和稳定性。通过深入的试验研究,旨在为盐湖铝系提锂吸附剂的工业应用提供科学、可操作的制备工艺和关键性能优化方向,推动相关领域的技术进步与产业发展。

粉体铝基吸附剂在制盐高硝母液中提锂的应用研究

文章采用新型粉体铝系吸附剂,以盐硝联产排放的高硝母液为研究对象,通过小试和中试实验,探究吸附剂对制盐高硝母液的适用性及其吸附容量和循环性能等,探索最佳吸附工艺条件,并根据实验结果为工程产业化设计提供依据。

氢氧化锂结晶母液中铊金属的高效脱除研究

以8%铁基纳米悬浮剂作吸附剂,能够高效、便捷并具有选择性地去除氢氧化锂结晶母液中的铊(Tl)元素。实验结果表明:向500 mL氢氧化锂结晶母液(Li含量为10~17 g/L)中加入30 mL 8%铁基纳米悬浮剂,搅拌1 h,能够完全去除氢氧化锂结晶母液中的Tl元素。此外,氢氧化锂结晶母液经吸附和过滤后,滤液静置24 h后会产生红褐色的絮状物,再次过滤并检测结果显示其主要成分为Fe(OH)_(3)。

磁性粒子Fe_(3)O_(4)@SiO_(2)掺杂铝基锂吸附剂的制备及性能研究

用Fe_(3)O_(4)@SiO_(2)磁性粒子和铝基吸附剂复合制备一种层状磁性铝基吸附剂(MLDHs),利用XRD、SEM等对MLDHs的结构形貌进行表征。考察了MLDHs对溶液中锂离子的吸附性能,研究了吸附过程的吸附等温线、吸附动力学以及循环稳定性。结果表明:MLDHs适合在p H为3~5的溶液中进行锂吸附,其吸附容量最高达到12.42 mg/g。在混合离子溶液中,MLDHs对锂离子表现出良好的选择性和优先吸附。经过5次吸附-解吸循环后,MLDHs的吸附容量未发生明显变化。吸附等温线和吸附动力学分别符合Langmuir模型和准二级动力学模型。

An ultrathin and continuous Li_4Ti_5O_(12) coated carbon nanofiber interlayer for high rate lithium sulfur battery

Severe capacity fading and poor high rate performance of lithium sulfur(Li–S) battery caused by "shuttle effect" and low conductivity of sulfur hampers its further developments and applications. Li_4Ti_5O_(12) (LTO)possesses high lithium ion conductivity, and it is also can be used as an active adsorbent for polysulfide. Herein, fine LTO particle coated carbon nanofibers(CNF) were prepared and a conductive network both for electron and lithium ion was built, which can greatly promote the electrochemical conversion of polysulfide and improve the rate performance of Li–S batteries. Meanwhile, a quantity of adsorption sites is constructed by defects of the surface of LTO-CNF membrane to effectively immobilize polysulfide. The multifunctional LTO-CNF interlayer could impede the shuttle effect and enhance comprehensive electrochemical performance of Li–S batteries, especially high rate performance. With such LTO-CNF interlayer,the Li–S battery presents a specific capacity of 641.9 mAh/g at 5 C rate. After 400 cycles at 1 C, a capacity of 618.0 mAh/g is retained. This work provides a feasible strategy to achieve high performance of Li–S battery for practical utilization.

Preparation and adsorption performance of multi-morphology H_(1.6)Mn_(1.6)O_(4) for lithium extraction

In this paper,a lithium-ion sieve(LIS)with different morphologies,such as rod-like(LIS-R),spherical(LIS-S),flower-like(LIS-F),and three-dimensional macroporous-mesoporous(LIS-3D),was prepared by hydrothermal synthesis,solid reaction,and hard-template synthesis.The results showed that the LIS with different morphologies presented great differences in specific surface area,pore volume,adsorption selectivity,and structure stability.LIS-3D with highest specific surface area and pore volume displayed the maximum adsorption capacity and adsorption rate,but the stability of LIS-3D was poor because of the manganese dissolution.By comparison,LIS-S has the best structural stability while maintaining a satisfactory adsorption capacity(35.02 mg·g^(-1))and adsorption rate.The LIS-S remained about 90%of the original adsorption capacity after five cycles of adsorption-desorption process.In addition,in the simulated brine system(the magnesium to lithium ratio of 400),the LIS-S exhibited the highest selectivity(α_(Mg)^(Li))of 425.14.In sum,the LIS-S with good morphology is a potential adsorbent for lithium extraction from brine.

Synthesis and Characterization of Lithium Manganese Oxide with Different Ratio of Mole on Lithium Recovery Process from Ge-othermal Fluid of Lumpur Sidoarjo

Geothermal fluid of Lumpur Sidoarjo (Lusi) with lithium content as high as 5.81 mg/liter has a great potential as the source of lithium. Lithium recovery from geothermal liquid of Lusi is firstly investigated by adsorption methods with Lithium Manganese Oxide (LMO) as absorbent. LMO is considered as a promising candidate of adsorbent material due to non-toxic and low cost production. LMOs with different ratio of mole are prepared by solid state reactions method at temperature 500?C for 5 hrs. XRD peaks of pre- and post-acid treatment LMO 1, 0.8 and 0.5 show a stable spinel crystal structure while LMO 2 has monoclinic structure. The highest lithium adsorption capability is obtained by LMO 1 with 6.6 mg/g.

盐湖提锂尾液中锂回收的吸附试验研究

从高镁锂比盐湖提锂生产尾液中回收锂,可实现锂资源高效回收利用,对企业经济效益的提高具有重要意义。以东台吉乃尔盐湖提锂尾液为原料,系统性研究了铝系层状锂吸附剂JW-LAHS对提锂尾液中锂的静态、动态吸附和解吸过程。结果表明,吸附剂的静态吸附容量为7.3 mg/g,镁锂分离因子为27.98;最佳动态吸附条件为床层高度24.8 cm,进料流速3.5 mL/min,此时穿透时间为22.0 min,Li+吸附率大于95%,饱和时间为210 min,饱和吸附容量达到5.5 mg/g,表明锂吸附剂适合从高镁锂比提锂尾液中回收锂。BDST模型能够准确预测床层穿透时间,误差小于8.61%。使用去离子水进行解吸,增大解吸流速能够加速Li+脱出,但对Mg^(2+)的解吸无明显影响。解吸流速为4.6 mL/min,解吸360 min时,Li+解吸率为83.25%,总解吸液的镁锂比值为0.7,仅为提锂尾液(80)的0.88%。循环20次后吸附容量仍能保持原来的82%以上,表明锂吸附剂循环稳定性良好。

铝基锂吸附剂分离高钠型地下卤水锂资源过程研究

铝基锂吸附剂由于其解吸条件温和,不发生溶损,是目前唯一一种成功实现工业化生产的盐湖卤水提锂吸附剂,然而其在高钠型地下卤水中的应用可行性还有待考察。使用实验室自制的H-LDHs颗粒吸附剂,系统研究了吸附液进料流速、解吸温度及解吸液中离子浓度对固定床吸附和解吸过程的影响,实验结果表明,在高钠卤水中,当进料流速从1 BV/h(1 BV/h=0.170 L/h)增加到4 BV/h时,穿透时间缩短了79%,而穿透吸附容量仅降低了17.8%。升高解吸温度可显著提高固定床的Li+解吸量,而增大解吸液中的Na+浓度会抑制Li+的解吸。此外,开发了分段循环解吸工艺,并将其用于四川某地实际地下卤水提锂过程,该工艺能够有效实现解吸工段固定床出料液中Li+的富集。

铝基吸附剂固定床分离卤水锂资源过程研究

铝基锂吸附剂是一种非常适用于低锂品位、高镁锂比盐湖卤水提锂的吸附剂,具有无溶损、稳定性高等优点,也是目前唯一一种已投入工业化生产的吸附剂。使用自制的球形铝基锂吸附剂GLDH填充固定床,系统研究了吸附温度、进料流速、初始锂离子浓度和床层高度对GLDH固定床分离卤水锂资源过程中吸附穿透曲线的影响。结果表明:升高温度、增加床层高度、降低初始锂离子浓度和进料流速会导致穿透时间延长、穿透吸附容量升高。采用BDST、Clark、Thomas、Y-N和M-D-R 5种经验模型对锂吸附穿透曲线进行拟合,确定M-D-R模型能够较准确地描述固定床锂吸附过程。

盐湖卤水吸附提锂技术研究进展

随着科技与经济的快速发展,传统资源的提取已无法满足当今新能源产业的需求,锂作为新能源的支柱性资源更是研究热点之一。文中列举了目前国内外盐湖资源状况,介绍了盐湖卤水中吸附提锂工艺的原理和研究现状,其以能耗低、成本低、绿色无污染等显著优势逐渐成为未来获取锂资源的重要方向,综合分析了锰钛系离子筛和铝系层状吸附剂的吸附与解吸机理以及循环稳定性能。简要综述了膜吸附和电化学吸附两类新型锂资源开发技术,并对未来吸附工艺的优化进行展望。

钛系离子筛用于盐湖卤水锂提取的研究进展

锂资源是国家战略资源,我国盐湖锂丰富,从盐湖中高效提取锂具有重大意义。在盐湖提锂的各种方法中,吸附法具有选择性高、经济性好、工艺成熟度高的优势,发展高性能的吸附材料是该方法的关键,其中钛系离子筛被认为是很有发展前景的一类吸附材料。全面综述了近年来钛系离子筛用于盐湖卤水提锂的研究进展,重点阐述了钛系离子筛的结构、吸附机理、合成与改性方法以及成型方法,对钛系离子筛应用中存在的问题进行了分析、归纳,对其未来发展方向进行了展望,以期充分挖掘钛系离子筛的优势,实现其在盐湖提锂中的规模化应用。