The rechargeable aluminum-ion battery

We report a novel aluminium-ion rechargeable battery comprised of an electrolyte containing AlCl(3) in the ionic liquid, 1-ethyl-3-methylimidazolium chloride, and a V(2)O(5) nano-wire cathode against an aluminium metal anode. The battery delivered a discharge capacity of 305 mAh g(-1) in the first cycle and 273 mAh g(-1) after 20 cycles, with very stable electrochemical behaviour.     

Electrospun V2O5 nanostructures with controllable morphology as high-performance cathode materials for lithium-ion batteries

Porous V(2)O(5) nanotubes, hierarchical V(2)O(5) nanofibers, and single-crystalline V(2)O(5) nanobelts were controllably synthesized by using a simple electrospinning technique and subsequent annealing. The mechanism for the formation of these controllable structures was investigated. When tested as the cathode materials in lithium-ion batteries (LIBs), the as-formed V(2)O(5) nanostructures exhibited a highly reversible capacity, excellent cycling performance, and good rate capacity. In particular, the porous V(2)O(5) nanotubes provided short distances for Li(+)-ion diffusion and large electrode-electrolyte contact areas for high Li(+)-ion flux across the interface; Moreover, these nanotubes delivered a high power density of 40.2?kW?kg(-1) whilst the energy density remained as high as 201?W?h?kg(-1), which, as one of the highest values measured on V(2)O(5)-based cathode materials, could bridge the performance gap between batteries and supercapacitors. Moreover, to the best of our knowledge, this is the first preparation of single-crystalline V(2)O(5) nanobelts by using electrospinning techniques. Interestingly, the beneficial crystal orientation provided improved cycling stability for lithium intercalation. These results demonstrate that further improvement or optimization of electrochemical performance in transition-metal-oxide-based electrode materials could be realized by the design of 1D nanostructures with unique morphologies.     

Li-biphenyl-1,2-dimethoxyethane solution: calculation and its application

Metallic lithium reacts with biphenyl in 1,2-dimethoxyethane (DME) solvent at room temperature. This reaction has been studied using density functional theory (DFT) at the B3LYP level together with the 6-311++G (d,p) basis set. From the energy results of the corresponding optimized geometries for intermediate complexes, the reaction can be interpreted as a charge-transfer process between lithium and biphenyl followed by Li+ coordination with ether oxygens in DME. In addition, the experimentally observed vibrational bands can be unambiguously assigned and interpreted according to the normal modes calculated for the biphenyl-Li-DME complex. This organic complex solution has been demonstrated as a very effective chemical lithiation agent. V2O5 can be lithiated up to 1.45 lithium ions per formula. The lithiated V2O5 shows a high Li-extraction capacity of 173 mAh/g as cathode material for lithium ion batteries.     

锂离子电池用富锂层状正极材料

正极材料与负极材料是锂离子电池重要组成部分。目前锂离子电池负极材料比容量通常在300mAh/g以上,而正极材料比容量始终徘徊在150mAh/g。正极材料正在成为锂离子电池性能进一步提升的瓶颈。富锂层状正极材料是一类新型正极材料,其可逆容量在200mAh/g以上,其高容量特性引起人们的广泛关注。这类材料可以用xLi₂MO₃·(1-x)LiM'O₂ (M 为Mn, Ti, Zr之一或任意组合; M'为Mn, Ni, Co之一或任意组合; 0≤x≤1)形式表示。由于其组成与结构的特殊性,这类富锂层状正极材料的充放电机理也不同于其它含锂过渡金属氧化物正极材料。本文介绍富锂层状正极材料的合成、结构与充放电机理,重点介绍近年来通过改性提高其电化学性能方面的研究进展,指出目前富锂材料研究中存在的问题,探讨未来的研究重点。     

P(VdF-HFP)-基离子液体复合聚合物电解质的阴极稳定性及热稳定性

以聚偏氟乙烯-六氟丙烯P(VdF-HFP)聚合物为基体, 制备了含离子液体1-甲基-3-乙基咪唑六氟磷酸盐(EMIPF6)、用于锂离子电池的离子液体复合聚合物电解质[P(VdF-HFP)/LiPF₆/EMIPF₆/EC(碳酸乙烯酯)-PC(碳酸丙烯酯)]. 采用热重分析法以及燃烧实验测试了复合聚合物电解质的热稳定性. 离子电导率测试表明, 离子液体的存在显著改善了复合聚合物电解质的离子传输; 循环伏安测试表明, 添加剂EC和PC的加入提高了复合电解质的阴极稳定性, 制得的离子液体复合聚合物电解质在0.3-4.3 V 电压范围内稳定存在. Li₄Ti₅O₁₂ 和LiCoO₂为电极材料、P(VdF-HFP)/LiPF₆/EMIPF₆/EC-PC 为电解质的半电池表现出优良的循环性能, 0.1C充放电倍率下, Li/LiCoO₂和Li/Li₄Ti₅O₁₂半电池的可逆容量分别为130和144 mAh·g^-1. 但EC、PC在一定程度上降低了离子液体复合聚合物电解质的热稳定性.     

Fe2O3 xerogel used as the anode material for lithium ion batteries with excellent electrochemical performance

A new strategy was applied to synthesise a porous nanostructure of α-Fe(2)O(3) xerogel assembled from nanocrystalline particles (～5 nm) with abundant mesopores (～3 nm) using a hydrothermal method. The α-Fe(2)O(3) xerogel exhibits excellent cycling performance (up to 1000 cycles) and rate capability (reversible discharging capacity 280 mAh g(-1) at 10 C) as a potential anode for high power lithium-ion batteries.     

Binder-free carbon fiber/TiNb2O7 composite electrode as superior high-rate anode for lithium ions batteries

Carbon fibre supported titanium niobium oxide (TiNb₂O₇) composite electrodes are prepared via a simple solvothermal method and show superior high-rate performance with large capacity and good cycling performance.     

层状钒青铜纳米片的制备及其锂离子电池阳极材料性能

室温下, 在水溶液中将铵根离子和水分子插入到商用V₂O₅纳米颗粒的层间, 制得了层状的钒青 铜[(NH₄)₂V₆O₁₆·H₂O]纳米片. 该纳米片的尺寸为2~10 μm, 厚度为50~250 nm. 与商用V₂O₅纳米颗粒相比, (NH₄)₂V₆O₁₆·H₂O纳米片用作锂离子电池(LIBs)的阳极材料时, 其性能得到较大提升, 包括大的可逆放电容量 (0.1 A/g时为1148 mA·h/g)、 出色的循环性能(循环70圈后在0.1 A/g时具有1002 mA·h/g的高容量)和高倍率性能(在0.1 A/g时具有1070 mA·h/g的可逆性能). 研究结果表明, (NH₄)₂V₆O₁₆·H₂O纳米片可以作为锂离子电池优良的阳极材料, 也有望应用于其它(如钠离子电池和锌离子电池等)可再充电电池.     

S/In_2O_3纳米材料的制备及其在锂硫电池正极材料中的应用

以硝酸铟和蔗糖为原料,依次经水热反应和550℃碳化制得In_2O_3纳米材料(nano-In_2O_3);将硫渗入nanoIn_2O_3得S/In_2O_3,其结构和微观形貌经SEM,TEM和XRD表征。将S/In_2O_3,导电炭黑和聚偏氟乙烯按质量比8∶1∶1制成正极材料(1);将1涂覆于铝箔上,锂片作参比电极,1 mol·L~(-1)LiPF_6的DMF/DOL(V/V=1/1)溶液为电解液,组装成锂硫半电池。采用循环伏安法和恒电流充放电法研究了S/In_2O_3的电化学性能。结果表明:在1.95 V和2.3 V处有两个还原峰,2.5 V处有一个氧化峰。电流密度为335 m A·g~(-1),首次放电比容量为1 357m Ah·g~(-1),库伦效率为82.75%。经80次充放电后,放电比容量为537 m Ah·g~(-1)。     

Effects of thermal annealing on the Li(+) intercalation properties of V(2)O(5) x nH(2)O xerogel films

V(2)O(5) x nH(2)O xerogel films with n = 1.6, 0.6, and 0.3 have been prepared from the sol-gel route by reacting V(2)O(5) with H(2)O(2) followed by drying under ambient conditions and thermal annealing at 110 and 250 degrees C, respectively. After dehydration, V(2)O(5) crystallizes at 300-330 degrees C, as revealed by thermal gravimetric analysis and X-ray diffraction. Electrochemical characterization demonstrated that V(2)O(5) x 0.3H(2)O film exhibits the best Li(+) intercalation performance, with an initial capacity of 275 mAh/g and a stabilized capacity of 185 mAh/g under a high current density of 100 microA/cm(2) after 50 cycles. Under a low current density of 10 microA/cm(2), the capacity of this film can reach 390 mAh/g. Such an enhanced electrochemical property by thermal treatment is ascribed to the reduced water content, the retained interlayer spacing, and the dominant amorphous phase in the film.     

锂离子电池正极材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2在LiNO_3溶液中的电化学性能研究

由溶胶凝胶法合成的锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2在水溶液体系中具有优异的高倍率充放电性能,放电时能够输出极高功率密度.XRD表征证明合成的LiNi1/3Co1/3Mn1/3O2材料具有层状α-NaFeO2结构,SEM形貌显示材料的粒径约为500nm,恒电流充放电测试表明LiNi1/3Co1/3Mn1/3O2材料在pH12的2mol·L-1LiNO3溶液中,以2C(0.36A/g)倍率充放时,比容量达到了147mAh/g.如以80C(14.4A/g)、150C(27A/g)和220C(39.6A/g)的倍率充放,材料的比容量仍可达到64mAh/g、33mAh/g和16mAh/g,而全电池的功率密度分别达到2574W/kg、3925W/kg、4967W/kg.其中80C倍率充放,经1000周循环后,容量保持率为90.9%.     

Synergetic ternary metal oxide nanodots-graphene cathode for high performance zinc energy storage

Zinc-based electrochemistry energy storage with high safety and high theoretical capacity is considered to be a competitive candidate to replace lithium-ion batteries. In electrochemical energy storage, multi-metal oxide cathode materials can generally provide a wider electrochemical stability window and a higher capacity compared with single metal oxides cathode. Here, a new type of cathode material, MnFe₂Co₃O₈ nanodots/functional graphene sheets, is designed and used for aqueous hybrid Zn-based energy storage. Coupling with a hybrid electrolyte based on zinc sulfate and potassium hydroxide, the as-fabricated battery was able to work with a wide electrochemical window of 0.1∼1.8 V, showed a high specific capacity of 660 mAh/g, delivered an ultrahigh energy density of 1135 Wh/kg and a scalable power density of 5754 W/kg (calculated based on the cathode), and displayed a long cycling life of 1000 cycles. These are mainly attributed to the valence charge density distribution in MnFe₂Co₃O₈ nanodots, the good structural strengthening as well as high conductivity of the cathode, and the right electrolyte. Such cathode material also exhibited high electrocatalytic activity for oxygen evolution reaction and thus could be used for constructing a Zn-air battery with an ultrahigh reversible capacity of 9556 mAh/g.     

Full structural and electrochemical characterization of Li2Ti6O13 as anode for Li-ion batteries

A detailed structural and electrochemical study of the ion exchanged Li(2)Ti(6)O(13) titanate as a new anode for Li-ion batteries is presented. Subtle structural differences between the parent Na(2)Ti(6)O(13), where Na is in an eightfold coordinated site, and the Li-derivative, where Li is fourfold coordinated, determine important differences in the electrochemical behaviour. While the Li insertion in Na(2)Ti(6)O(13) proceeds reversibly the reaction of lithium with Li(2)Ti(6)O(13) is accompanied by an irreversible phase transformation after the first discharge. Interestingly, this new phase undergoes reversible Li insertion reaction developing a capacity of 170 mAh g(-1) at an average voltage of 1.7 V vs. Li(+)/Li. Compared with other titanates this result is promising to develop a new anode material for lithium ion rechargeable batteries. Neutron powder diffraction revealed that Na in Na(2)Ti(6)O(13) and Li in Li(2)Ti(6)O(13) obtained by Na/Li ion exchange at 325 °C occupy different tunnel sites within the basically same (Ti(6)O(13))(2-) framework. On the other hand, electrochemical performance of Li(2)Ti(6)O(13) itself and the phase released after the first full discharge is strongly affected by the synthesis temperature. For example, heating Li(2)Ti(6)O(13) at 350 °C produces a drastic decrease of the reversible capacity of the phase obtained after full discharge, from 170 mAh g(-1) to ca. 90 mAh g(-1). This latter value has been reported for Li(2)Ti(6)O(13) prepared by ion exchange at higher temperature.     

Sandwich-type functionalized graphene sheet-sulfur nanocomposite for rechargeable lithium batteries

A functionalized graphene sheet-sulfur (FGSS) nanocomposite was synthesized as the cathode material for lithium-sulfur batteries. The structure has a layer of functionalized graphene sheets/stacks (FGS) and a layer of sulfur nanoparticles creating a three-dimensional sandwich-type architecture. This unique FGSS nanoscale layered composite has a high loading (70 wt%) of active material (S), a high tap density of ～0.92 g cm(-3), and a reversible capacity of ～505 mAh g(-1) (～464 mAh cm(-3)) at a current density of 1680 mA g(-1) (1C). When coated with a thin layer of cation exchange Nafion film, the migration of dissolved polysulfide anions from the FGSS nanocomposite was effectively reduced, leading to a good cycling stability of 75% capacity retention over 100 cycles. This sandwich-structured composite conceptually provides a new strategy for designing electrodes in energy storage applications.     

High-Voltage Rechargeable Alkali–Acid Zn–PbO2 Hybrid Battery

Aqueous rechargeable batteries have attracted attention owning to their advantages of safety, low cost, and sustainability, while the limited electrochemical stability window (1.23 V) of water leads to their failure in competition with organic-based lithium-ion batteries. Herein, we report an alkali–acid Zn–PbO₂ hybrid aqueous battery obtained by coupling an alkaline Zn anode with an acidic PbO₂ cathode. It shows the capability to deliver an impressively high open-circuit voltage (V_oc) of 3.09 V and an operate voltage of 2.95 V at 5 mA cm⁻², thanks to the contribution of expanding the voltage window and the electrochemical neutralization energy from the alkali–acid asymmetric-electrolyte hybrid cell. The hybrid battery can potentially deliver a large area capacity over 2 mAh cm⁻² or a high energy density of 252.39 Wh kg⁻¹ and shows almost no fading in area capacity over 250 charge–discharge cycles.     

聚并苯二次电池的研究

聚乙炔在电解质中能进行电化学可逆的离子掺杂和脱掺杂,以聚乙炔膜作为电极的活性物质,用PVDF、LiClO_4-PC薄膜作为电解质,制作了可充式全塑电池,但由于聚乙炔在空气中稳定性差,电池的放电性能还不理想,目前,除聚苯胺电池在日本已有商品外,其它几种聚合物电池还都处于实验室研究开发阶段,用聚并苯半导体材料分别为正负极制做的全塑电池,自放电小,循环寿命可达3000次,是有实用价值的聚合物二次电池之一,前文对酚醛树脂的热解过程、产物结构、电学性质及导电机制等进行了研究,本文研究了用聚并苯材料做锂二次电池的正极活性物质、高氯酸锂(溶解在碳酸丙烯酯中,1 mol/L)为电解质的二次电池性能。     

A solvothermal pre-oxidation strategy converting pitch from soft carbon to hard carbon for enhanced sodium storage

Due to its low cost and easy availability, the pitch is considered a promising precursor for soft carbon anodes. However, pitch-derived soft carbon shows a high graphitization degree and small interlayer spacing, resulting in its much lower sodium storage performance than hard carbon. We propose a novel pre-oxidation strategy to introduce additional oxygen atoms into the low-cost soft carbon precursor pitch to fabricate a defect-rich and large-interlayer spacing hard carbon anode (HPP-1100). Compared with the direct pyrolysis of pitch carbon, the sodium storage capacity of HPP-1100 is significantly improved from 120.3 mAh/g to 306.7 mAh/g, with an excellent rate and cycling capability (116.5 mAh/g at 10 C). Moreover, when assorted with an O3-Na(NiFeMn)_1/3O₂ cathode, the full cell delivers a high reversible capacity of 274.0 mAh/g at 0.1 C with superb cycle life. This work provides a new solution for realizing the application of low-cost pitch anodes in Na-ion batteries.     

High-performance nitrogen and sulfur co-doped nanotube-like carbon anodes for sodium ion hybrid capacitors

Sodium ion hybrid capacitors are of great concern in large-scale and cost-effective electrical energy storage owing to their high energy and power densities, as well as natural abundance and wide distribution of sodium. However, it is difficult to find a well-pleasing anode material that matches the high-performance cathode materials to achieve good energy and power output for sodium ion hybrid capacitors. In this paper, nitrogen and sulfur co-doped nanotube-like carbon prepared by a simple carbonization process of high sulfur-loaded polyaniline nanotubes is introduced as the anode. The assembled sodium ion half cell based on the optimal nanotube-like carbon delivers a high reversible capacity of ∼304.8 mAh/g at 0.2 A/g and an excellent rate performance of ∼124.8 mAh/g at 10 A/g in a voltage window of 0.01–2.5 V (versus sodium/sodium ion). For the hybrid capacitors assembled using the optimal nanotube-like carbon as the anode and high-capacity activated carbon as the cathode, high energy densities of ∼100.2 Wh/kg at 250 W/kg and ∼50.69 Wh/kg at 12,500 W/kg are achieved.     

Free-standing vanadium pentoxide nanoribbon film as a high-performance cathode for rechargeable sodium batteries

Vanadium pentoxide(V_2O_5·nH_2O) nanoribbons are synthesized via a hydrothermal process. These ribbons are 20 nm thick, 200 nm to 1 μm wide and several tens of micrometers long. Free-standing binder-free films are prepared by using these nanoribbons with multi-walled carbon nanotubes(MWCNTs) and used as the cathode for rechargeable sodium batteries. The large interlayer space between the V_2O_5 bilayers can enhance the kinetics of sodium ion intercalation/deintercalation. In addition, the intertwining network of the V_2O_5·0.34 H_2O film provides efficient electron conduction pathways and shortens diffusion distances of sodium ion. The electrochemical tests prove that the freestanding V_2O_5 · 0.34 H_2O film cathode delivers high reversible specific capacities(190 mAh/g) and good cycling stabilities(170 mAh/g after 150 cycles) in the voltage range between 1.5 V and 3.5 V.     

A Bipolar and Self‐Polymerized Phthalocyanine Complex for Fast and Tunable Energy Storage in Dual‐Ion Batteries

Bipolar redox organics have attracted interest as electrode materials for energy storage owing to their flexibility, sustainability and environmental friendliness. However, an understanding of their application in all‐organic batteries, let alone dual‐ion batteries (DIBs), is in its infancy. Herein, we propose a strategy to screen a variety of phthalocyanine‐based bipolar organics. The self‐polymerizable bipolar Cu tetraaminephthalocyanine (CuTAPc) shows multifunctional applications in various energy storage systems, including lithium‐based DIBs using CuTAPc as the cathode material, graphite‐based DIBs using CuTAPc as the anode material and symmetric DIBs using CuTAPc as both the cathode and anode materials. Notably, in lithium‐based DIBs, the use of CuTAPc as the cathode material results in a high discharge capacity of 236 mAh g^?1 at 50 mA g^?1 and a high reversible capacity of 74.3 mAh g^?1 after 4000 cycles at 4 A g^?1. Most importantly, a high energy density of 239 Wh kg^?1 and power density of 11.5 kW kg^?1 can be obtained in all‐organic symmetric DIBs.