Synthesis, characterization, and electrochemical application of Ca(OH)2-, Co(OH)2-, and Y(OH)3-Coated Ni(OH)2 tubes

We report on the synthesis, characterization, and electrochemical application of Ca(OH)2-, Co(OH)2-, and Y(OH)3-coated Ni(OH)2 tubes with mesoscale dimensions. These composite tubes were prepared via a two-step chemical precipitation within an anodic alumina membrane under ambient conditions. The morphology and structure of the as-synthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM) equipped with energy dispersive spectroscopy (EDS). The results showed that the size of the tubes was of mesoscale dimension and the proportion of the tube morphology was about 95%. The as-prepared composite tubes were further investigated as the positive-electrode materials of rechargeable alkaline batteries. Electrochemical measurements revealed that the Ni(OH)2 tubes coated with Ca(OH)2, Co(OH)2, and Y(OH)3 exhibited superior electrode properties including high discharge capacity, excellent high-temperature and high-rate discharge ability, and good cycling reversibility. The mechanism analysis suggests that both the coated layers and the unique hollow-tube structures play an indispensable role in optimizing the electrochemical performance of nickel hydroxide electrodes.     

锂硫电池中钴磷共掺杂MoS2催化性能的第一性原理研究

基于第一性原理计算, 探究了未掺杂、 Co单掺杂、 Co, P共掺杂MoS₂表面上多硫化物的吸附和转化, 揭示了Co, P共掺杂对MoS₂材料吸附能力和催化能力的影响. 研究结果表明, 共掺杂使得MoS₂吸附能力增强, 特别是对产物Li₂S的稳定吸附提供了多硫化物转化动力, 进而增强了催化能力. Co, P共掺杂表面与长链、 中链、 短链多硫化物之间均存在Li—S和S—P双重成键, 具备最大的吸附能力; 另一方面, 共掺杂表面对于产物Li₂S的显著稳定化作用降低了多硫化物转化过程中解离步骤的能量需求, 增大了转化过程的能量释放, 为多硫化物转化提供了驱动力. 上述两方面因素共同增强了MoS₂的催化活性, 有效抑制了穿梭效应, 提升了电池的电化学性能.     

锂氧电池双功能还原石墨烯-LaFeO_3复合纳米催化剂的制备及性能

制备具有氧还原(ORR)与氧释放(OER)双功能催化活性的特殊孔道结构电催化剂是锂氧电池研究的挑战之一。本文以氧化石墨烯、硝酸铁、硝酸镧、柠檬酸为原料,结合溶胶凝胶和水热合成方法,制备出还原氧化石墨烯(RGO)与铁酸镧(LaFeO_3)复合的双功能催化剂(RGO-LaFeO_3)。X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱和Raman光谱分析结果确认该复合催化剂由纯相钙钛矿结构LaFeO_3和还原氧化石墨烯组成,扫描电子显微镜(SEM)观察到LaFeO_3纳米颗粒均匀地负载在RGO片层表面。锂氧电池测试结果指出,相对于LaFeO_3纳米粒子(NP-LaFeO_3),RGO-LaFeO_3催化剂具有更好的ORR和OER催化活性,归因于RGO特殊的三维导电多孔结构与LaFeO_3纳米粒子的协同催化作用。以RGO-LaFeO_3作为阴极催化剂的锂氧电池在限1000 m Ah?g~(-1)比容量、100 m A?g~(-1)电流密度条件下,可实现36周稳定的充放电循环,展示出良好的应用前景。     

Co_3O_4 modified Ag/g-C_3N_4 composite as a bifunctional cathode for lithium-oxygen battery

Rechargeable lithium-oxygen(Li-O_2)batteries have appeal to enormous attention because they demonstrate higher energy density than the state-of-the-art Li-ion batteries.Whereas,their practical application is impeded by several challenging problems,such as the low energy round trip efficiencies and the insufficient cycle life,due to the cathode passivation caused by the accumulation of discharge products.Developing efficient catalyst for oxygen reduction and evolution reactions is effective to reduce the overpotentials in Li-O_2cells.In our work,we report a Co_3O_4modified Ag/g-C_3N_4nanocomposite as a bifunctional cathode catalyst for Li-O_2cells.The g-C_3N_4substrate prevents the accumulation of Ag and Co_3O_4nanoparticles and the presence of Ag NPs improves the surface area of g-C_3N_4and electronic conductivity,significantly improving the oxygen reduction/evolution capabilities of Co_3O_4.Due to a synergetic effect,the Ag/g-C_3N_4/Co_3O_4nanocomposite demonstrates a higher catalytic activity than each individual constituent of Co_3O_4or Ag/g-C_3N_4for the ORR/OER on as catalysts in Li-O_2cells.As a result,the Ag/gC_3N_4/Co_3O_4composite shows impressive electrochemical performance in a Li-O_2battery,including high discharge capacity,small gap between charge and discharge potential,and high cycling stability.     

A Co(OH)2−graphene nanosheets composite as a high performance anode material for rechargeable lithium batteries

A Co(OH)₂?graphene nanosheets (Co(OH)₂?GNS) composite as a high performance anode material was firstly prepared through a simultaneous hydrothermal method. The structure, morphology and electrochemical performance of the obtained samples were systematically investigated by X-ray diffraction (XRD), transmission electron microscope (TEM) and electrochemical measurements. According to the TEM analysis, the surface of the Co(OH)₂ is surrounded with GNS in the Co(OH)₂?GNS composite. The specific discharge (lithiation) and charge (delithiation) capacities of Co(OH)₂?GNS attain to 1599 and 1120 mAh/g at a current density of 200 mA/g in the first cycle, respectively. After 30 cycles, the reversible capacity of Co(OH)₂?GNS is still 910 mAh/g with the retention of 82%. The particular structure of Co(OH)₂ particles surrounded by the GNS could limit the volume change during cycling and provide an excellent electronic conduction pathway, which could be the main reason for the remarkable improvement of electrochemical performance.     

Nanocrystalline nickel cobalt hydroxides/ultrastable Y zeolite composite for electrochemical capacitors

A novel nanocomposite of Co(OH)₂−Ni(OH)₂ and ultrastable Y molecular sieves was synthesized by an improved chemical precipitation method for electrochemical capacitors. The Co(OH)₂−Ni(OH)₂/ultrastable Y zeolite (USY) composite and its microstructure were characterized by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. Electrochemical characterization was performed by cyclic voltammetry and galvanostatic charge–discharge measurements. The results show that Co(OH)₂−Ni(OH)₂/USY microstructure applied for the electrochemical energy storage has displayed superior capacitive performance. The effect of heat treatment conditions on specific capacitance properties was also systemically explored. Upon annealing at 250 °C, the maximum specific capacitance was up to 479 F/g (or 1,710 F/g after correcting for the weight percent of Co(OH)₂−Ni(OH)₂ phase). Annealing temperatures higher than 250 °C may cause the hydroxide to form oxide phase and decrease the surface activity of the oxide, thereby leading to a decline of the specific capacitance.     

共沉积铝镍氢氧化物的结构及电化学特性

为了改善Ni(OH)2的电化学性质,提高锌镍电池的充放电性能,用化学共沉淀法合成了混合铝镍氢氧化物Ni/Al(OH)x.用XRD和FTIR表征了Ni/Al(OH)x样品的晶体结构及IR光谱特征;测试了用Ni/Al(OH)x为正极活性物质的Zn/Ni实验电池的充放电性能.研究结果表明:所合成的Ni/Al(OH)x具有α-Ni(OH)2的晶体结构;Ni/Al(OH)x活性物质在充放电过程中主要为γ/α循环,以Ni/Al(OH)x作为正极活性物质的Zn/Ni试验电池具有优良的循环性能,其最高放电比容量为379mA·h/g.     

LiCoO2对LiMn2-xMxO4正极材料的混合改性研究

采用机械混合层状LiCoO2和经过多元掺杂改性后尖晶石型LiMn2-xMxO4(M=Co Cr La,x=nCo nCr nLa,且0相似文献   

Fabrication of Co(OH)2 coated Pt nanoparticles as an efficient catalyst for chemoselective hydrogenation of halonitrobenzenes

Co(OH)(2) coated platinum nanoparticles Pt/Co(OH)(2) were prepared by microwave assistance and hydrothermal method, and the prepared samples were composed of Pt nanoparticles with an average size of 1.8 nm coated uniformly in the thin Co(OH)(2) leaves based on the results of X-ray diffraction, transmission electron microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy. The Pt/Co(OH)(2) presented excellent catalytic performance in the chemoselective hydrogenation of halonitrobenzenes such as chloronitrobenzenes, bromonitrobenzene and iodonitrobenzene, and above 99.6% selectivity to haloanilines was achieved at complete conversion irrespective of the substrates used, even for iodonitrobenzene to which the dehalogenation is more easily to occur. Co(OH)(2) was confirmed to prohibit the dehalogenation effectively, and the Pt/Co(OH)(2) catalyst could be recycled for several times.     

表面覆CoOOH的球形Ni(OH)2的制备及快充性能

应用化学沉淀-电化学氧化法,于球形N i(OH)2颗粒表面生成CoOOH包覆层,研究包覆处理对AA型高容MH/N i电池快充性能的影响,并由红外光谱和扫描电镜表征覆钴样品.结果表明,以包覆CoOOH的N i(OH)2作正极活性材料装配的电池较之于正极单一添加CoO的电池,其内阻降低了约3.4 mΩ,该电池快充时充电电压平台较低且在充电末期电池温度不超过55℃,首次放电效率达90.6%,快充循环寿命达300周次.     

Strategies with Functional Materials in Tackling Instability Challenges of Non-aqueous Lithium-Oxygen Batteries

The instabilities of the battery including cathode corrosion/passivation,shuttling effect of the redox mediators,Li anode corrosion,and electrolyte decomposition are major barriers toward the practical implementation of lithium-oxygen(Li-O2)batteries.Functional materials offer great potential in high performance Li-O2 batteries owing to their functional tailorability of chemical modification for alleviating side reactions and improving catalysis activity,well-defined properties for discharge products storage,and fast mass and electron transfer paths.In this review,instability problems of non-aqueous Li-O2 batteries and recent studies related to the functional materials in tackling the instability issues from rational cathode construction,inhibition of redox mediators(RMs)shuttling,anode protection and novel electrolyte design are illustrated.Future research directions to overcome the critical issues are also proposed for this promising battery technology.The instability issues and the related strategies with functional materials based on the comprehensive consideration of all battery components proposed in this review provide the systematic,deep understanding and rational design of functional materials for Li-O2 batteries,which is beneficial to achieving the practical Li-O2 batteries.     

Nature-inspired Three-dimensional Au/Spinach as a Binder-free and Self-standing Cathode for High-performance Li-O2 Batteries

Design and fabrication of functional porous air cathode materials with superior catalytic activity is still the key point for non-aqueous lithium-oxygen(Li-O₂) batteries. Herein, inspired by the self-standing three-dimensional(3D) structure of the natural spinach leaves, a unique binder-free and self-standing porous Au/spinach cathode for high-performance Li-O₂ batteries has been developed. The carbonized spinach leaves serve as a superconductive current collector and an ideal porous host for accommodating catalysts. The Au/spinach cathode could offer enough spaces for accommodating the discharge products, shorten the distance of the oxygen and electrolyte diffusion, and promote the oxygen reduction reaction(ORR) and oxygen evolution reaction (OER) processes. This optimized Au/spinach cathode achieved a high specific area capacity of 7.23 mA‧h/cm² at a current density of 0.05 mA/cm² and exhibited excellent stability(280 cycles at 0.05 mA/cm² with a fixed capacity of 0.2 mA‧h/cm²). The superior performance encourages the construction of more advanced cathode architectures by the use of bio-composites for Li-O₂ batteries.     

单层镍锰层状双金属氢氧化物用于锂-氧电池双功能催化剂

将块体镍锰层状双金属氢氧化物(Ni_3Mn-LDHs)通过液相剥离法制备成单层Ni_3Mn-LDHs,然后采用自组装法获得Ni_3MnLDHs/CNT复合材料。采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)对复合材料的结构进行分析,通过恒流充放电、循环伏安(CV)和电化学阻抗谱(EIS)研究电极的电化学过程。结果表明:Ni_3Mn-LDHs/CNT复合材料可以有效提升ORR和OER的催化活性,与CNT正极相比较,Ni_3Mn-LDHs/CNT正极在锂-氧电池中的放电容量提高了近300%,并且具有优异的倍率性能和循环稳定性。     

实时磁性测试深入理解锂离子电池中的过渡金属催化作用

催化剂由于具有降低电化学过电位和改善动力学条件的能力,在各种储能器件中起着至关重要的作用.在锂离子电池中,首圈放电过程中形成的固体电解质界面膜,通常被认为是一旦形成就稳定不分解的.而在过渡金属的催化下,这种电解质分解衍生的聚合物凝胶状膜(PGF)能可逆地形成和分解.这种过渡金属催化机制可以进行催化储锂,即形成的PGF具...     

Cobalt–Manganese Mixed‐Sulfide Nanocages Encapsulated by Reduced Graphene Oxide: In Situ Sacrificial Template Synthesis and Superior Lithium Storage Properties

This work demonstrates a facile in situ synthesis of cobalt–manganese mixed sulfide (CoMn‐S) nanocages on reduced graphene oxide (RGO) sheets by using a crystalline Co–Mn precursor as the sacrificial template. The CoMn‐S/RGO hybrid was applied as the anode for Li‐ion storage and exhibited superior specific capacity, excellent cycling performance, and great rate capability. In particular, lithium storage testing revealed that the hybrid delivered high discharge–charge capacities of 670 mA h g⁻¹ at 1.0 A g⁻¹ after 400 cycles and 925 mA h g⁻¹ at 0.1 A g⁻¹ after 300 cycles. The outstanding electrochemical performance of CoMn‐S/RGO is attributed to the close entanglement of nanocages with RGO nanosheets achieved by the synthetic method, which greatly improves ion/electron transport along the interfaces and efficiently mitigates volume dilation during lithium reactions. This rational design of both the composition and architecture of mixed metal sulfides can be expanded to other composite systems for high‐capacity Li‐ion batteries and provides a unique insight into the development of advanced hybrid electrode materials.     

不同载体负载的Cu2(OH)3CI催化剂对甲醇氧化羰基化的催化性能

采用浆液浸渍法制备了小同载体负载的Cu2(OH)3Cl催化剂,考察了催化剂对甲醇氧化羰基化合成碳酸二甲酯(DMC)反应的催化性能.结果表明,各载体负载的Cu2(OH)3Cl催化剂活性均高于传统的负载CuCl2催化剂;以比表面积较大的活性炭(AC)为载体的催化剂活性最高.以Cu2(OH)3Cl/AC(w(Cu)=18.71%)为催化剂时,甲醇转化率、DMC选择性和DMC时宅收率可分别达到6.93%,67.3%和139.1mg/(g·h);其催化性能比较稳定,反应60h后其催化活性略有下降.通过CO程序升温脱附、X射线衍射、X射线光电子能谱和扫描电镜等技术对催化剂进行了表征.结果表明,在反应过程中催化剂的活性物种Cu2(OH)3Cl的晶粒逐渐团聚、长大,并且转化为CuCl2和CuO;同时,新鲜催化剂中唯一的CuⅡ物种部分转化为CuⅠ物种.     

Ethylene sulfite based electrolyte for non-aqueous lithium oxygen batteries

Non-aqueous lithium–oxygen(Li–O_2) batteries have been considered as the superior energy storage system due to their high-energy density, however, some challenges limit the practical application of Li–O_2 batteries. One of them is the lack of stable electrolyte. In this communication, a novel electrolyte with ethylene sulfite(ES) used as solvent for Li–O_2 batteries was reported. ES solvent showed low volatility and high electrochemical stability. Without a catalyst in the air-electrode of Li–O_2 batteries, the batteries showed high specific capacity, good round-trip efficiency and cycling stability.     

三维网状结构Ru/石墨烯/碳纳米管复合材料作为锂氧电池正极催化剂的性能

利用物理浸渍和冷冻干燥等方法制备了具有三维网状结构的Ru/石墨烯/碳纳米管复合材料, 对该材料的结构、 形貌及电化学性能进行了表征和研究. 结果表明, 当Ru含量为30%, 热处理温度为500 ℃时, 材料的催化性能最优. 将其用作锂氧电池的正极催化剂, 以50 mA/g电流密度进行首次充放电时, 放电比容量约为5800 mA·h/g, 且在放电比容量为4000 mA·h/g以内时, 其极化电压仅为0.9 V; 当以50 mA/g电流密度进行恒容(500 mA·h/g)充放电循环时, 在极化电压低于1.1 V时, 仍能稳定循环12周. 复合材料电催化机理的研究结果表明, 三维网状结构不仅提供了O₂和Li⁺的传输通道, 更增加了放电产物Li₂O₂的储存场所. 金属钌纳米粒子的负载既增加了复合材料的反应活性位点, 又促进了放电产物Li₂O₂的分解.     

石墨烯氢氧化钴复合催化剂的一步合成及其对酸性橙的催化降解

用一步合成自组装法制备出了氢氧化钴与还原氧化石墨烯（Co（OH）₂/rGO）的复合催化剂,并将其用于水中染料的催化降解实验. 通过X射线衍射（XRD）,激光拉曼（Raman）光谱,透射电镜（TEM）,X射线能量色散谱（EDS）以及X射线光电子能谱（XPS）等一系列分析手段对催化剂的结构形貌进行了详细的表征,表征结果证实氢氧化钴很好地附着在还原石墨烯的表面. 最后初步考察了催化剂催化单过硫酸钾（PMS）降解酸性橙（AO7）的性能. 结果表明,催化剂显示出了高效的催化性能,酸性橙的色度可在12 min内完全去除,总有机碳（TOC）实验也表明染料降解的同时也可获得较高的矿化度. 循环稳定性实验表明在进行到第三次实验时,催化剂仍能保持高的催化活性,将酸性橙在16 min内降解完毕.     

Synthesis and characterization of Co(OH)<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> nanotube composites as supercapacitor materials

A novel composite of Co(OH)₂ and TiO₂ nanotubes was synthesized by a chemical precipitation method. Co(OH)₂/TiO₂ nanotube composites and its microstructure were characterized by transmission electron microscopy (TEM), X-ray diffraction pattern (XRD). The electrochemical capacitance performance of this composite was investigated by cyclic voltammetry and charge–discharge tests with a three-electrode system in 6 M KOH solution. We synthesized different weight ratios of Co(OH)₂/TiO₂ nanotubes, a maximum specific capacitance of 229 F/g was obtained for the composite. Based on these tests, we propose that TiO₂ nanotubes provide the three-dimensional nanotube network structure for the composite and make the Co(OH)₂ dispersed. For these reasons, the TiO₂ nanotubes used as a framework for Co(OH)₂ improve the utilization of Co(OH)₂ greatly.