Fabrication of cobalt aluminum-layered double hydroxide nanosheets/carbon spheres composite as novel electrode material for supercapacitors

A new design route was presented to fabricate cobalt aluminum-layered double hydroxide(CoAl-LDH)thin layers whichgrow on carbon spheres(CSs)through a growth method.The CoAl-LDH thin layers consist of nanoflakes with a thickness of20nm.The galvanostatic charge-discharge test of the CoAl-LDH/CSs composite shows a great specific capacitance of1198F/g at1A/g(based on the mass of the CoAl-LDH/CSs composite)in6mol/L KOH solution,and the composite displays an impressive specificcapacitance of920F/g even at a high current density of10A/g.Moreover,the composite remains a specific capacitance of928F/gafter1000cycles at2A/g,and the specific capacitance retention is84%,indicating that the composite has high specific capacitance,excellent rate capability and good cycling stability in comparison to pristine CoAl-LDH.

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.

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。

层状双羟基氢氧化物及其衍生物在锂硫电池中的应用

锂硫电池具有超高的理论能量密度、较低的材料成本,是极有前途的下一代储能体系。但硫导电性差、充放电过程中的穿梭效应、体积膨胀、负极锂枝晶等问题造成锂硫电池的比容量低、容量衰减严重、库仑效率差,影响了其实际应用。层状双羟基氢氧化物(LDHs)是一种二维材料,具有可调节的插层结构、可控的表面化学性质和独特的拓扑转换特性,作为储能材料受到了广泛的关注。LDHs对多硫化物具有良好的约束能力,作为锂硫电池正极硫载体可以高效吸附和催化充放电过程中产生的多硫化物,减少多硫化物的迁移,加快氧化还原反应动力学,从而提升锂硫电池的电化学性能。此外,二维LDHs可涂覆于隔膜作为正极与隔膜间的中间层,通过物理作用阻挡多硫化物向负极的迁移,抑制穿梭效应;LDHs用于锂负极可以促进金属锂的均匀成核和沉积。目前LDHs在锂硫电池中应用广泛,本文综述了LDH及其衍生物在锂硫电池中的应用优势,介绍了其在锂硫电池正极、中间层、负极中的应用现状,指出了LDHs材料在锂硫电池中的发展方向。

镍钴水滑石纳米笼/GO复合材料在锂离子电池负极中的应用

近年来,水滑石(LDH)材料因其组成、结构和形貌易于调节,具有丰富的活性位点,被认为是高性能锂离子电池(LIBs)负极的替代材料,然而水滑石作为负极仍存在电导率差和结构易聚集等问题.于此同时,金属有机框架(MOFs)及碳基材料也由于其优秀的孔隙率、比表面积以及良好的电导率在储能领域得到了广泛的关注.考虑到这二者有望对LDH的主要缺陷有所改进,提出了将原位沉淀、化学刻蚀法和静电吸附法相结合,使镍钴水滑石纳米笼(H-(Ni,Co)-LDHP)能够固定在GO上,从而得到镍钴水滑石纳米笼/氧化石墨烯复合材料(H-(Ni,Co)-LDHP/GO).这种GO上密集分布的中空纳米结构更能有效抑制水滑石纳米片的聚集,并有利于锂离子的脱嵌.H-(Ni,Co)-LDHP/GO纳米复合材料作为锂离子电池的负极,在电流密度为50m A·g^(-1)下,循环第一圈库伦效率可达68%,循环50圈后电容保留率为68.4%.

AlLi-LDH中Al-O八面体环吸附锂的机制

采用共沉淀法合成铝锂层状双氢氧化物(AlLi-LDH)并进行提锂试验。AlLi-LDH的空间群为P32或C2/m,微观形貌呈直径为5~10μm的规则球形。AlLi-LDH吸附Li^(+)后,空间群转化为P32。当Li^(+)浓度为95.4 mg/L时,1 h后锂吸附量为8.98 mg/g;吸附48 h后,吸附量增加到16.50 mg/g;根据二级吸附模型预测Li^(+)吸附总量为17.57 mg/g。当Mg^(2+)/Li^(+)的质量比为1067时,Mg^(2+)/Li^(+)分离系数为29536。空间群为P32时,Li-O的相互作用强度变弱,且相互作用属于静电效应。具有P32空间基团的AlLi-LDH更容易吸附和解吸Li^(+)。

A metal nitride interlayer for long life lithium sulfur batteries

With the growing concerns on global energy crisis and the greenhouse effect,the exploration on renewable energy and related emerging energy conversion and storage technologies are highly interested [1].Lithium sulfur (Li–S) battery system receives great attention for its high theoretical specific energy(2600 Wh/kg),which is deemed to be a promising candidate as next generation high energy density batteries [2].

Synthesis and Characterization of Methanesulfonate and Ethanesulfonate Intercalated Lithium Aluminum LDHs

LDH-phases become increasingly interesting due to their broad ability to be able to incorporate many different cations and anions. The intercalation of methanesulfonate and ethanesulfonate into a Li-LDH as well as the behavior of the interlayer structure as a function of the temperature is presented. A hexagonal P63/m [LiAl2(OH)6][Cl?1.5H2O] (Li-Al-Cl) precursor LDH was synthesized by hydrothermal treating of a LiCl solution with γ-Al(OH)3. This precursor was used to intercalate methanesulfonate (CH3O3S?) and ethanesulfonate (C2H5O3S?) through anion exchange by stirring Li-Al-Cl in a solution of the respective organic Li-salt (90?C, 12 h). X-ray diffraction pattern showed an increase of the interlayer space c' (d001) of Li-Al-methanesulfonate (Li-Al-MS) with 1.2886 nm and Li-Al-ethanesulfonate (Li-Al-ES) with 1.3816 nm compared to the precursor with 0.7630 nm. Further investigations with Fourier-transform infrared spectroscopy and scanning electron microscopy confirmed a complete anion exchange of the organic molecules with the precursor Cl?. Both synthesized LDH compounds [LiAl2(OH)6]CH3SO3?nH2O (n = 2.24-3.72 (Li-Al-MS) and [LiAl2(OH)6]C2H5SO3}?nH2O (n = 1.5) (Li-Al-ES) showed a monomolecular interlayer structure with additional interlayer water at room temperature. By increasing the temperature, the interlayer water was removed and the interlayer space c' of Li-Al-MS decreased to 0.87735 nm (at 55?C). Calculations showed that a slight displacement of the organic molecules is necessary to achieve this interlayer space. Different behavior of Li-Al-ES could be observed during thermal treatment. Two phases coexisted at 75?C - 85?C, one with a reduced c' (0.9015 nm, 75?C) and one with increased c' (1.5643 nm, 85?C) compared to the LDH compound at room temperature. The increase of c' is due to the formation of a bimolecular interlayer structure.

铝系成型锂吸附剂性能测试评价与对比

我国察尔汗盐湖卤水中蕴含丰富的锂资源,但总体品位较低,具有锂浓度低、镁锂比高的特点,导致开发难度很大。吸附法是针对高镁锂比卤水进行提锂的有效方法,其中铝系锂吸附剂具有洗脱无溶损的优势,目前已在盐湖提锂工业中应用。分别对两种工业化铝系锂吸附剂A、B以及实验室自制吸附剂C进行了系统化表征与吸附性能评价。实验结果显示三种成型吸附剂的有效成分均是锂铝层状氢氧化物,在静态吸附条件下,25℃时吸附剂A、B、C对察尔汗老卤中锂的吸附量分别为2.23、0.45、4.90 mg·g^(-1),吸附动力学均符合拟二级动力学方程,不同温度下吸附等温线拟合结果表明Sips三参数模型能够准确描述三种吸附剂的吸附过程。

3003铝合金翅片在冷却液中耐蚀性的研究

采用电感耦合等离子体质谱(ICP-MS)、金相显微镜、扫描电镜(SEM)等技术分析了风力发电机用冷却液使用前后离子种类和浓度的变化对3003铝合金耐蚀性的影响。在3.5%NaCl溶液中以动电位极化曲线和电化学阻抗谱(EIS)研究了单宁酸、鸟嘌呤、2−氨基噻唑、葡甘露聚糖、二乙基二硫代氨基甲酸钠等缓蚀剂对3003铝合金的缓蚀性能。结果显示2−氨基噻唑最好,缓蚀效率高达90.3%。分别以上述5种缓蚀剂为锂铝类水滑石(LiAl-LDHs)的插层剂,通过水热法在3003铝合金表面制备出不同的LiAl-LDHs/缓蚀剂复合转化膜。电化学测量结果显示,LiAl-LDHs/2−氨基噻唑复合转化膜的耐蚀性最好,且比单独使用2−氨基噻唑缓蚀剂或LiAl-LDHs转化膜时强。

Ca(ALG)_2-LiCl·2Al(OH)_3·nH_2O的合成研究

聚氯乙烯常被用于吸附剂造粒,由于聚氯乙烯水溶性差,所以吸附时间比较长。本文首次采用沉淀法合成了LiCl·2Al(OH)_3·nH_2O,以海藻酸钙为载体制备了Ca(ALG)_2-LiCl·2Al(OH)_3·nH_2O微球。通过单因素实验确定了LiCl·2Al(OH)_3·nH_2O最佳的合成条件。实验结果表明:反应温度80℃、Al^(3+)/Li^+=1.5、OH^-/Al^(3+)=2.5、吸附剂∶载体=2∶1为前躯体最佳的合成条件,吸附量可达15.02 mg/g。吸附剂微球透水性能好,可以实现快速达到吸附饱和的目的,且吸附剂对水体不造成危害。

水滑石基电极材料的结构调控及电化学储能应用研究进展

水滑石是一种具有层板金属阳离子可搭配、层间客体可替代和高分散性的二维层板状纳米材料,在能量存储与转换应用领域获得广泛的关注和研究。但由于水滑石自身存在容易聚集和电导率差并且在电化学循环过程中易粉化的问题,因此需对水滑石基电极材料进行针对性结构设计,从而提高其电化学性能。系统介绍了水滑石材料的结构与性质特点和当下对其结构调控的研究进展。另外,还详细介绍了其在电化学储能领域的应用进展,主要包括锂离子电池和超级电容器电极材料领域,并展望了今后的研究趋势。

钴铝双金属氧化物的制备及其储锂性能的研究

以水滑石为前驱体,采用微波辅助合成法,制备复合水滑石前驱体材料(CoAl-LDHs),该前驱体是由超薄纳米片组成。经焙烧处理后,得到多孔纳米花球状Co_(3)O_(4)/Al_(2)O_(3)复合材料。研究结果表明,电极在0.2 A/g的电流密度下,经过100次循环之后仍能表现较好的稳定性且倍率性能良好,在为光伏电站配置锂离子电池储能系统的材料选择上提供可能。

锂-氧电池用石墨烯/层状双金属氢氧化物纳米复合材料的制备及性能研究

为有效提升锂氧电池的电化学性能,以钴铝复合金属氢氧化物(Co Al-LDH)作为催化剂,研究其对锂空气电池性能的影响.采用工艺简单、成本低廉的共沉淀法将其与石墨烯复合后,制备出r GO/Co Al-LDH纳米复合材料,并将其应用于锂氧电池.采用X射线衍射、拉曼光谱、同步热分析和扫描电镜对材料结构进行表征,利用恒流充放电测试、交流阻抗测试(EIS)和线性伏安扫描(LSV)对电池电化学性能进行表征.研究结果表明:制备得到的纳米复合材料可明显提升氧还原反应(ORR)的催化活性,首次放电容量达到2 662 m A·h·g^(-1),与单纯石墨烯相比提高了51.5%,同时充电电位降低了430 m V.循环过程中电池库伦效率较高,电池循环性能得到显著改善.

石墨烯包覆材料的制备及电化学性能探究

为减少水滑石(Layered Double Hydroxide,LDH)用作电极材料时的体积膨胀效应造成电化学性能衰减,本文利用石墨烯纳米片包覆CoNi-LDH制备复合材料。该材料被用作负极材料时,比容量相对于LDH有明显的改善。在电流密度为0.05和2.0 A·g^(-1)时,所达到的首次放电容量是1388、495 mAh·g^(-1)。在0.05 A·g^(-1)的电流密度下,经过20个循环仍保持近乎70%的容量保持率。

一种同时回收镍和负极石墨制备超级电容器材料的方法

以废旧的锂电池和化学镀镍废液为主要原料,制备了氧化石墨烯/镍铝双羟基复合金属氧化物复合材料。采用X-射线衍射仪、场发射电子显微镜和电化学方法对该复合材料进行了表征。研究表明,该复合材料呈现为网络状的纳米片,其表面具有特殊微孔结构。在1.0A/g电流密度下,复合材料电极的比电容可达1 184.3F/g;经过200次充/放电循环测试后,复合材料的比电容保持率仍可达98.3%,具有良好的充/放电循环稳定性。