亚微米LiFe0.05Mn1.95O4正极材料的制备及电化学性能

采用固相燃烧法合成了亚微米单晶多面体LiFe_0.05Mn_1.95O₄正极材料。借助XRD、FE-SEM、TEM、XPS和恒电流充放电等手段对样品的结构、形貌、物相组成和电化学性能进行测试。结果表明,Fe掺杂未改变尖晶石型LiMn₂O₄的立方晶系结构,其{400}和{440}衍射峰相对应的晶面出现显著的择优生长,形成了形貌为{111}、{110}和{100}晶面的单晶去顶角八面体晶粒。LiFe_0.05Mn_1.95O₄正极材料表现出比纯LiMn₂O₄材料更为优异的电化学性能,在1C和5C时有着114.7mA·h/g、104.7mA·h/g首次放电比容量,10C倍率下经1000次循环后,容量保持率为83.9%。循环伏安与阻抗分析得出掺杂后的样品有着较大的锂离子扩散系数与较小的活化能。对5C倍率循环1000次后Fe掺杂样品的极片分析发现,其晶体结构基本无变化,适量的Fe掺杂能够有效抑制尖晶石型LiMn₂O₄在充放电循环过程中的Jahn-Teller效应以及Mn的溶解,提升材料的结构稳定性与容量保持率。     

聚丙烯腈/聚酯无纺布微孔复合锂电隔膜的制备及性能

为了改善锂电隔膜的耐热性、电解液亲和性和机械性能,本文以聚丙烯腈为主要材料,采用相转化法制备了聚酯无纺布支撑的聚丙烯腈微孔复合锂电隔膜,对隔膜的理化性能（孔道结构、机械性能、电解液性能和耐热性）和电池性能（循环性能、倍率性能）进行系统研究。结果表明,复合隔膜具有均匀的微孔结构,平均孔径约为425nm,孔隙率为74%,拉伸强度为30MPa;电解液亲和性良好,吸液率为385%,接触角接近0°,锂离子电导率较市售隔膜显著提高,达到1.65mS/cm;在150℃、0.5h的热处理条件下,复合隔膜的热收缩率为0。鉴于良好的理化特性,该隔膜所装配的钴酸锂/锂金属电池表现出优异的循环容量和倍率容量保持性,如在0.2C倍率下,经历200次循环后电池的放电容量保持率为95.2%,在10C倍率下电池的放电容量为0.5C倍率下的58.3%。因此,相转化法制备的聚丙烯腈基微孔复合隔膜在锂离子电池中显示出较好的应用前景。     

一种水性负极黏结剂的合成及性能

黏结剂对电极的性能有着重要的影响。本文设计并制备了一种新型水性聚(乙烯-乙烯醇)-磺酸锂（EVOH-SO₃Li,简称ES-Li）电极黏结剂,并对其键接结构及组成进行分析;对其溶解性、电解液稳定性、热稳定性进行测试;对所制电极柔性、微观形貌及电化学性能进行研究。经与聚(乙烯-乙烯醇)（EVOH）及商业的聚偏氟乙烯（PVDF）黏结剂进行对比。结果表明：ES-Li水性黏结剂具有不溶解于电解液,热稳定性良好等优点;ES-Li黏结剂制备负极柔性及微观形貌优良,采用ES-Li作为负极黏结剂的电池在电化学稳定窗口、界面阻抗、首次循环效率、循环及倍率等方面均表现优异,ES-Li负极的首次库仑效率为89.93%,在1C下循环100次的容量保持率为96.93%,且在2C、5C倍率下的循环性能均优于EVOH及PVDF制备的负极,具有应用潜力及商业化前景。     

Amorphous silicon–carbon based nano-scale thin film anode materials for lithium ion batteries

The buffering effect of carbon on the structural stability of amorphous silicon films, used as an anode for lithium ion rechargeable batteries, has been studied during long term discharge/charge cycles. To this extent, the electrochemical performance of a prototype material consisting of amorphous Si thin film (∼250 nm) deposited by radio frequency magnetron sputtering on amorphous carbon (∼50 nm) thin films, denoted as a-C/Si, has been investigated. In comparison to pure amorphous Si thin film (a-Si) which shows a rapid fade in capacity after 30 cycles, the a-C/Si exhibits excellent capacity retention displaying ∼0.03% fade in capacity up to 50 cycles and ∼0.2% after 50 cycles when cycled at a rate of 100 μA/cm² (∼C/2) suggesting that the presence of thin amorphous C layer deposited between the Cu substrate and a-Si acts as a buffer layer facilitating the release of the volume induced stresses exhibited by pure a-Si during the charge/discharge cycles. This structural integrity combined with microstructural stability of the a-C/Si thin film during the alloying/dealloying process with lithium has been confirmed by scanning electron microscopy (SEM) analysis. The buffering capacity of the thin amorphous carbon layer lends credence to its use as the likely compliant matrix to curtail the volume expansion related cracking of silicon validating its choice as the matrix for bulk and thin film battery systems.     

Improving electrochemical performance of NiO films by electrodeposition on foam nickel substrates

NiO films for lithium-ion batteries were deposited on copper plates and foam nickel substrates by electrodeposition and subsequent heat treatment at 300 °C. At a discharge/charge rate of 0.1 C, foam NiO films delivered reversible capacity larger than 650 mAh g⁻¹ and capacity retention over 93% after 50 cycles. NiO films deposited on foam nickel exhibited higher reversible capacity, better cyclability, as well as higher rate capability than those on copper plates. The unique three-dimensionally porous morphologies of foam NiO films were responsible for the better electrochemical performance, which provided not only high electrode/electrolyte contact area but also a good electronic conduction matrix. The present finding offers a new pathway for the large scale fabrication of high-energy-density electrodes for lithium-ion batteries.     

Enhanced high-potential and elevated-temperature cycling stability of LiMn2O4 cathode by TiO2 modification for Li-ion battery

The surface of spinel LiMn₂O₄ was modified with TiO₂ by a simple sol–gel method to improve its electrochemical performance at elevated temperatures and higher working potentials. Compared with pristine LiMn₂O₄, surface-modification improved the cycling stability of the material. The capacity retention of TiO₂-modified LiMn₂O₄ was more than 85% after 60 cycles at high potential cycles between 3.0 and 4.8 V at room temperature and near to 90% after 30 cycles at elevated temperature of 55 °C at 1C charge–discharge rate. SEM studies shows that the surface morphology of TiO₂-modified LiMn₂O₄ was different from that of pristine LiMn₂O₄. Powder X-ray diffraction indicated that spinel was the only detected phase in TiO₂-modified LiMn₂O₄. Introduction of Ti into LiMn₂O₄ changed the electronic structures of the particle surface. Therefore a surface solid compound of LiTi_xMn_2−xO₄ may be formed on LiMn₂O₄. The improved electrochemical performance of surface-modified LiMn₂O₄ was attributed to the improved stability of crystalline structure and the higher Li⁺ conductivity.     

Morphology effect on the electrochromic and electrochemical performances of NiO thin films

NiO thin films on ITO substrate were prepared by chemical bath deposition (CBD) and sol–gel method, respectively. The microstructure and morphology of the NiO films were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Both the films have polycrystalline cubic NiO, but have distinct morphology. The CBD NiO thin film with a highly porous structure exhibited a noticeable electrochromic performance. The variation of transmittance was high up to 82% at 550 nm and the coloration efficiency (CE) was calculated to be 42 cm² C⁻¹. The sol–gel NiO thin film with a smoothly compact structure presented 35% and 28 cm² C⁻¹ at 550 nm, respectively. The electrochemical properties of both the NiO thin films were investigated in 1 M KOH electrolyte by means of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements. The CV and EIS measurements revealed that the CBD NiO thin film had better electrochemical reversibility, higher reactivity and reaction kinetics due to its highly porous structure.     

Simple and rapid synthesis of NiO/PPy thin films with improved electrochromic performance

Nickel oxide/polypyrrole (NiO/PPy) thin films were deposited by a two step process in which the NiO layer was electrodeposited potentiostatically from an aqueous solution of NiCl₂·6H₂O at pH 7.5 on fluorine doped tin oxide (FTO) coated conducting glass substrates, followed by the deposition of polypyrrole (PPy) thin films by chemical bath deposition (CBD) from pyrrole mixed with ammonium persulfate (APS). The NiO/PPy films were further characterized for their structural, optical, morphological and electrochromic properties. X-ray diffraction study indicates that the films composed of polycrystalline NiO and amorphous PPy. Infrared transmission spectrum reveals chemical bonding between NiO and PPy. Rectangular faceted grains were observed from scanning electron microscopy results. The electrochromic (EC) property of the film was studied using cyclic voltammogram (CV), chronoamperometry (CA) and optical modulation. The NiO/PPy presents superior EC properties than their individual counterparts. The coloration/bleaching kinetics (response time of few ms) and coloration efficiency (358 cm²/C) were found to be improved appreciably. The dramatic improvement in electrochemical stability (from about 500 c/b cycles for PPy to 10,000 c/b cycles for NiO/PPy) was observed. This work therefore demonstrates a cost-effective and simple way of depositing highly efficient, faster and stable NiO/PPy electrodes for EC devices.     

Spin coated versus dip coated electrochromic tungsten oxide films: Structure, morphology, optical and electrochemical properties

A sol-gel derived acetylated peroxotungstic acid sol encompassing 4 wt.% of oxalic acid dihydrate (OAD) has been employed for the deposition of tungsten oxide (WO₃) films by spin coating and dip coating techniques, in view of smart window applications. The morphological and structural evolution of the as-deposited spin and dip coated films as a function of annealing temperature (250 and 500 °C) has been examined and compared by Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD). A conspicuous feature of the dip coated film (annealed at 250 °C) is that its electrochromic and electrochemical properties ameliorate with cycling without degradation in contrast to the spin coated film for which these properties deteriorate under repetitive cycling. A comparative study of spin and dip coated nanostructured thin films (annealed at 250 °C) revealed a superior performance for the cycled dip coated film in terms of higher transmission modulation and coloration efficiency in solar and photopic regions, faster switching speed, higher electrochemical activity as well as charge storage capacity. While the dip coated film could endure 2500 color-bleach cycles, the spin coated film could sustain only a 1000 cycles. The better cycling stability of the dip coated film which is a repercussion of a balance between optimal water content, porosity and grain size hints at its potential for electrochromic window applications.     

微孔碳材料修饰的隔膜用于高性能锂硫电池

锂硫电池具有较高的能量密度,是有发展前景的能量存储体系之一。但“穿梭效应”严重制约了锂硫电池的实际应用,为解决该问题,本文通过简单的一步热解法合成了孔径均匀的微孔碳材料,探究了微孔碳材料修饰隔膜后对锂硫电池性能的影响。结果表明,制备的微孔碳材料孔径集中在0.56nm左右,修饰隔膜后不仅能够有效抑制“穿梭效应”的产生,还有利于加快锂离子的传输,确保正极一侧溶解的多硫化物的再次利用。在0.1C的电流密度下,采用微孔碳材料修饰隔膜的电池首次放电比容量为1359mAh/g,循环100次之后容量能保持在966mAh/g,而修饰之前的传统聚丙烯隔膜,循环100次之后的比容量仅为409mAh/g;在1C的电流密度下循环500圈后,采用微孔碳材料修饰隔膜的电池容量保持率为88%,表现出优异的循环稳定性。     

Characterization of Al-doped spinel LiMn2O4 thin film cathode electrodes prepared by Liquid Source Misted Chemical Deposition (LSMCD) technique

A novel process called Liquid Source Misted Chemical Deposition (LSMCD) was used to synthesize Al-doped LiMn₂O₄ cathode films for Lithium microbatteries. The cathode films were characterized by XRD, SEM, cyclic volatmmetry, and charge/discharge test. LiMn_1.8Al_0.2O₄ film crystallized at 800 °C in rapid thermal annealing (RTA) for 5 min under oxygen atmosphere exhibited more improved electrochemical rechargeability than spinel LiMn₂O₄ film because the substitution of Al³⁺ for Mn³⁺ increased Mn---O bonding strength in the spinel framework and suppressed the two-phase behavior of the unsubstituted spinel during the intercalation/deintercalation that is the origin of the failure mechanism in the 4 V region. As a result, LiMn_1.8Al_0.2O₄ film showed an initial discharge capacity of 52 μAh/cm² μm and no capacity fade over 100 cycles.     

Hierarchical NiO nanoflake coated CuO flower core–shell nanostructures for supercapacitor

In this work, we developed a simple and cost-effective approach to prepare the hierarchical NiO/CuO nanocomposite without any surfactant. The morphology and structure of the hybrid nanostructure was examined by focus ion beam scanning electron microscopy (FIB/SEM), X-ray diffraction spectroscopy (XRD) and high-resolution transmission electron microscopy (HRTEM). Furthermore, the electrochemical properties of the hierarchical NiO/CuO nanocomposite electrodes were elucidated by cyclic voltammograms, galvanostatic charge/discharge tests and electrochemical impedance spectroscopy in 6 M KOH electrolyte. The electrochemical results demonstrated that this unique NiO/CuO nanostructure exhibited a specific capacitance of 280 F g⁻¹ and excellent cycling stability (91.4% retention after 3000 cycles). The remarkable electrochemical performance coupled with the facile synthesis of the hierarchical NiO/CuO nanocomposite indicated the great application potential in supercapacitors.     

NiO/C nanocapsules with onion-like carbon shell as anode material for lithium ion batteries

The synthesis of NiO/C nanocapsules with NiO nanoparticles as the core and onion-like carbon layers as the shell is reported. The NiO/C nanocapsules deliver an initial discharge capacity of 1689.4 mAh g⁻¹ at 0.5 C and maintain a high reversible capacity of 1157.7 mAh g⁻¹ after 50 cycles compared to the NiO nanoparticles of 383.5 mAh g⁻¹. As an anode material for lithium ion batteries, the NiO/C nanocapsules exhibit a remarkable discharge capacity, a high rate charge–discharge capability and an excellent cycling stability. The improvements are ascribed to the fact that the onion-like carbon shells not only can provide enough voids to accommodate the volume change of NiO nanoparticles but also can prevent the formation of solid electrolyte interface (SEI) films on the surface of the NiO nanoparticles and hence the direct contact of Ni and SEI films upon lithium extraction.     

不同铝源对LiNi1/3Co1/3Mn1/3O2材料的包覆改性研究

分别以纳米氧化铝、氢氧化铝及异丙醇铝为原料,采用液相浸渍法对LiNi1/3Co1/3Mn1/3O2材料进行氧化铝包覆,考察不同包覆源在LiNi1/3Co1/3Mn1/3O2材料表面进行氧化铝包覆后对材料电化学性能的影响。SEM及XRD结果显示,产物为层状α-NaFeO2结构,氧化铝均匀包覆在LiNi1/3Co1/3Mn1/3O2材料表面。充放电性能测试结果表明,在3种铝源中,以异丙醇铝为包覆源的材料性能最佳：在3.0~4.6 V的电压下,0.1 C倍率下首次放电比容量为196.1 mA·h/g, 1 C下循环50周后容量保持率为95.6%。     

The effect of vacuum evaporation plating on phase structure and electrochemical properties of AB5–5 mass% LaMg3 composite alloy

In this paper, Cu, Al and Ni were plated on the AB₅–5 mass% LaMg₃ composite hydrogen storage alloy using a vacuum evaporation plating method. The phase structure and the electrochemical properties were investigated. The X-ray diffraction (XRD) analysis shows that the phase structure is not changed obviously after the plating Cu, Al and Ni on the composites. The electrochemical tests show that maximum discharge capacity, high rate dischargeability (HRD), dischargeability at low temperature and cyclic stability was improved by vacuum evaporation plating Cu, Al and Ni. Maximum of discharge capacity of the AB₅–5 mass% LaMg₃ composite alloy plating Ni can reach 351 mAh/g, which is 3.5% higher than that of the untreated. HRD at I_d = 1200 mA/g of the composite alloy plating Cu is 45.0% of that at 60 mA/g, which is 20.4% higher than the untreated. Discharge capacity of the composite alloy plating Cu at low temperature 233 K is 205 mAh/g, which is 57.3% of that at 298 K, and it is much higher than 36.8% of the untreated composites. The discharge capacity retention of the composite alloy plating Al after 200 cycles is 7.8% higher than the untreated.     

Effective enhancement of the electrochemical properties for Na2FeP2O7/C cathode materials by boron doping

In recent years, the composite materials based on polyanionic frameworks as secondary sodium ion battery electrode material have been developed in large-scale energy storage applications due to its safety and stability. The Na₂FeP₂O₇/C (theoretical capacity 97 mA·h·g^-1) is recognized as optimum Na-storage cathode materials with a trade-off between electrode performance and cost. In the present work, The Na₂FeP₂O₇/C and boron-doped Na₂FeP_2-BO₇/C composites were synthesized via a novel method of liquid phase combined with high temperature solid phase. The non-metallic element B doping not only had positive influence on the crystal structure stability, Na⁺ diffusion and electrical conductivity of Na₂FeP₂O₇/C, but also contributed to the high-value recycling of B element in waste borax. The structure and electrochemical properties of the cathode material were investigated via X-ray diffraction (XRD), scanning electron microscopy (SEM), The X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and charge/discharge cycling. The results showed that different amounts of boron doping had positive effects on the structure and electrochemical properties of the material. The initial charge/discharge performances of born doped materials were improved in comparison to the bare Na₂FeP₂O₇/C. The cycle performance of the Na₂FeP_1.95B_0.05O₇/C showed an initial reversible capacity of 74.8 mA·h·g^-1 and the high capacity retention of 91.8% after 100 cycles at 1.0 C, while the initial reversible capacity of the bare Na₂FeP₂O₇/C was only 66.2 mA·h·g^-1. The improvement of apparent Na⁺ diffusion and electrical conductivity due to B doping were verified by the EIS test and CVs at various scan rate. The experimental results from present work is useful for opening new insight into the contrivance and creation of applicable sodium polyanionic cathode materials for high-performance.     

WO3 membrane-encapsulated layered LiNi0.6Co0.2Mn0.2O2 cathode material for advanced Li-ion batteries

Despite Nickel-rich materials have all the advantages of high capacity, long cycle life and low cost, there is still a disadvantage that the capacity decreases rapidly as the number of cycles increases. In order to solve this problem, WO₃ was uniformly coated on the surface of LiNi_0.6Co_0.2Mn_0.2O₂ cathode materials by wet coating, and its cycling performance was greatly improved with the higher capacity. The coated materials were analyzed by X-ray diffraction(XRD), Scanning electron microscope (SEM), high resolution Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy(XPS). The results showed that the coating thickness was around 3.15?nm, and some tungsten ions were doped into the lattice of the near surface area of the LiNi_0.6Co_0.2Mn_0.2O₂ material. In addition, the results of charge-discharge test showed that 1?wt%WO₃ coating LiNi_0.6Co_0.2Mn_0.2O₂ had the best performance, and delivered a discharge capacity of 140 mAh g^?1 (the capacity retention rate is 84.8%) in the potential interval of 2.8–4.3?V at 1?C (1?C?=?165?mA?g^?1) after 200 cycles, while the bare cathode material only delivered a discharge capacity of 120 mAhg^?1 (the capacity retention rate is 75%). The phenomenon indicates that the WO₃ coating plays a role in inhibiting the harmful side reactions between the cathode material and the electrolyte, improving the electrochemical and structure stability of LiNi_0.6Co_0.2Mn_0.2O₂ cathode materials.     

Patterned Si thin film electrodes for enhancing structural stability

A patterned film (electrode) with lozenge-shaped Si tiles could be successfully fabricated by masking with an expanded metal foil during film deposition. Its electrochemical properties and structural stability during the charge-discharge process were examined and compared with those of a continuous (conventional) film electrode. The patterned electrode exhibited a remarkably improved cycleability (75% capacity retention after 120 cycles) and an enhanced structural stability compared to the continuous electrode. The good electrochemical performance of the patterned electrode was attributed to the space between Si tiles that acted as a buffer against the volume change of the Si electrode.     

ZnF2包覆对锂离子电池正极材料LiNi0.5Mn1.5O4的性能影响

本文用溶胶凝胶法制备了LiNi0.5Mn1.5O4正极材料,然后用ZnF2对其进行表面包覆。XRD测试表明,包覆处理没有影响材料的晶体结构,EDS、SEM和TEM测试表明,2wt%ZnF2在LiNi0.5Mn1.5O4表面形成了约7 nm厚的均匀包覆层。对未包覆、1wt%、2wt%、3wt%包覆后的材料进行电化学性能测试对比,发现包覆后都能减弱电解液与基体间的相互作用,较大地稳定电极表面,提高了材料的电化学性能。其中,2wt%ZnF2包覆样品表现出最佳的电化学性能,0.2 C倍率下循环200圈后,其放电比容量维持在109 mAh/g,容量保持率为79.7%;在10 C时,放电比容量依然高达102.1 mAh/g;5 C高倍率下循环500圈后,放电比容量维持在94.2 mAh/g,容量保持率为85.6%。     

Preparation and electrochemistry of NiO/SiNW nanocomposite electrodes for electrochemical capacitors

This paper studies nickel oxide/silicon nanowires (NiO/SiNWs) as composite thin films in electrodes for electrochemical capacitors. The SiNWs as backbones were first prepared by chemical etching, and then the Ni/SiNW composite structure was obtained by electroless plating of nickel onto the surface of the SiNWs. Next, the NiO/SiNW nanocomposites were fabricated by annealing Ni/SiNW composites at different temperatures in an oxygen atmosphere. Once the electrodes were constructed, the electrochemical behavior of these electrodes was investigated with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). In 2 M KOH solution, the electrode material was found to have novel capacitive characteristics. Finally, when the NiO/SiNW composites were annealed at 400 °C, the maximum specific capacitance value was found to be as high as 681 F g⁻¹ (or 183 F cm⁻³), and the probing of the cycling life indicated that only about 3% of the capacity was lost after 1000 charge/discharge cycles. This study demonstrated that NiO/SiNW composites were the optimal electrode choice for electrochemical capacitors.