Sn-based Intermetallic Compounds for Li-ion Batteries: Structures, Lithiation Mechanism, and Electrochemical Performances

On account of the lower theoretical capacity of the traditional graphite,the development of reliable anode materials with high capacity and energy density for application in lithium-ion batteries(LIBs)is zealously pursued to meet the ever-increasing power demands for portable mobile devices or(hybrid)electronic vehicles.

A simple model for diffusion-induced dislocations during the lithiation of crystalline materials

Assuming that the lithiation reaction occurs randomly in individual small particles in the vicinity of the reaction front, a simple model of diffusion- induced dislocations was developed. The diffusion-induced dislocations are con- trolled by the misfit strain created by the diffusion of solute atoms or the phase transformation in the vicinity of the reaction front. The dislocation density is proportional to the total surface area of the ＂lithiated particle＂ and inversely pro- portional to the particle volume. The diffusion-induced dislocations relieve the diffusion-induced stresses.

Synthesis of γ-LiV_2O_5/VO_2 mixture by thermal lithiation of vanadium (+4,+5) oxides

γ-LiV2O5/VO2 composites were synthesized through thermal lithiation reaction of mixed valence (+4, +5) vanadium oxides by lithium bromide. The phase evolution, morphology and discharge behavior at 500 ℃ were investigated by thermal gravimeter/differential thermal analysis (TG/DTA), X-ray diffraction(XRD), scanning electron microscopy(SEM) and specific surface analysis(BET). The mixed vanadium oxides are obtained from the pyrolytic decomposition of ammonium metavanadate, with V6O13 as main phase. Results show that the lithiation reaction begins at about 258 ℃, with γ-LiV2O5 and VO2(B) as the product. VO2(B) can transit to VO2(R) in the range of 400-500 ℃, following by grain growth and crystalline development with the increase of temperature and roasting time. The ratio of γ-LiV2O5 to VO2 can be modified by the additive content of lithium bromide. A lattice shearing model about the nucleation and growth of LixV2O5 and VO2(B) inside mixed valence (+4, +5) vanadium oxides (e.g. V6O13, V3O7) is speculated, which is relative to oxygen-/vacancy-diffusion and structural evolution inspired by lithium-insertion. The open-circuit voltage of 2.6 V is observed in the single cell of Li-B/LiCl-KCl/(γ-LiV2O5/VO2) at 500 ℃, and the specific capacities of 146 and 167 mA·h/g (cut-off voltage 1.4 V) are measured for the positive material at 100 mA/cm2 and 200 mA/cm2, respectively.

Lithiated Nafion-garnet ceramic composite electrolyte membrane for solid-state lithium metal battery

Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12(LLZAO)composite solid electrolyte(CSE)membrane with 30μm thickness was prepared for the first time.By employing X-ray photoelectron spectroscopy and transmission electron microscope,the interaction between LLZAO and Li-Nafion was investigated.It is found that the LLZAO interacts with the Li-Nafion to form a space charge layer at the interface between LLZAO and Li-Nafion.The space charge layer reduces the migration barrier of Li-ions and improves the ionic conductivity of the CSE membrane.The CSE membrane containing 10 wt%LLZAO exhibits the highest ionic conductivity of2.26×10-4 S cm-1 at 30℃among the pristine Li-Nafion membrane,the membrane containing 5 wt%,20 wt%,and 30 wt%LLZAO,respectively.It also exhibits a high Li-ion transference number of 0.92,and a broader electrochemical window of 0-+4.8 V vs.Li+/Li than that of 0-+4.0 V vs.Li+/Li for the pristine Li-Nafion membrane.It is observed that the CSE membrane not only inhibits the growth of Li dendrites but also keeps excellent electrochemical stability with the Li electrode.Benefitting from the above merits,the solid-state LiFePO4/Li cell fabricated with the CSE membrane was practically charged and discharged at 30℃.The cell exhibits an initial reversible discharge specific capacity of 160 mAh g-1 with 97%capacity retention after 100 cycles at 0.2 C,and maintains discharge specific capacity of 126 mAh g-1 after500 cycles at 1 C.The CSE membrane prepared with Li-Nafion and LLZAO is proved to be a promising solid electrolyte for advanced solid-state Li metal batteries.

A lithiated gel polymer electrolyte with superior interfacial performance for safe and long-life lithium metal battery

Rechargeable lithium metal batteries(LMBs)have gained much attention recently.However,the short lifespan and safety issues restrict their commercial applications.Here we report a novel gel polymer electrolyte(GPE)based on lithiated poly(vinyl chloride-r-acrylic acid)(PVCAALi)to realize dendritesuppressing and long-term stable lithium metal cycling.PVC chains ensure the quick gelation process and high electrolyte uptake,and lithiated PAA segments enable the increase of mechanical strength,acceleration of lithium-ion transmission and improvement of interfacial compatibility.PVCAALi GPE showed much higher mechanical strength compared with other free-standing GPEs in previous works.It displays a superior ionic conductivity of 1.50 m S cm^(-1) and a high lithium-ion transference number of 0.59 at room temperature.Besides,the lithiated GPE exhibits excellent interfacial compatibility with lithium metal anodes.Lithium symmetrical cells with PVCAALi GPE yield low hysteresis of 50 m V over1000 h at 1.0 m A cm^(-2).And the possible mechanism of the lithiated GPE with improved lithium-ion transfer and interfacial property was discussed.Accordingly,both the Li4Ti5O12/Li and lithium-sulfur(Li-S)cells assembled with PVCAALi GPE show outstanding electrochemical performance,retaining high discharge capacities of 133.8 m Ah g^(-1) and 603.8 m Ah g^(-1) over 200 cycles,respectively.This work proves excellent application potential of the highly effective and low-cost PVCAALi GPE in safe and long-life LMBs.

Enhanced Electrochemical Performance of Poly(ethylene oxide)Composite Polymer Electrolyte via Incorporating Lithiated Covalent Organic Framework

The lithiated covalent organic framework(named TpPa-SO_(3) Li),which was prepared by a mild chemical lithiation strategy,was introduced in poly(ethylene oxide)(PEO)to produce the composite polymer electrolytes(CPEs).Li-ion can transfer along the PEO chain or across the layer of TpPa-SO_(3) Li within the nanochannels,resulting in a high Li-ion conductivity of3.01×10^(-4)S/cm at 60℃.When the CPE with 0.75 wt.%TpPa-SO_(3) Li was used in the LiFePO_(4)‖Li solid-state battery,the cell delivered a stable capacity of 125 mA·h/g after 250 cycles at 0.5 C,60℃.In comparison,the cell using the CPE without TpPa-SO_(3) Li exhibited a capacity of only 118 mA·h/g.

A long-life and safe lithiated graphite-selenium cell with competitive gravimetric and volumetric energy densities

Lithium-selenium(Li-Se) battery is a promising system with high theoretical gravimetric and volumetric energy densities, while its long-term cyclability is hard to realize, especially when a practical Se cathode with high Se content, high Se loading, and high density is employed. The main obstacles are the sluggish conversion kinetics of the dense Se cathodes and the continuous deterioration of the Li-metal anodes.Here, by introducing an acetonitrile(AN)-based electrolyte and replacing the Li electrode with a lithiated graphite, we successfully build a hybrid conversion-intercalation system using a high-content(80 wt%),decent-loading(3.0 mg cm^(-2)), and low-porosity(44%) Se cathode. The as-designed lithiated graphite||Se(LG||Se) cell demonstrated a high Se utilization(97.4%), a long cycle life(3000 cycles), and an ultrahigh average Coulombic efficiency(99.98%). The cell also works well under lean-electrolyte(2 l L mg^(-1)) condition and shows outstanding safety performance in the nail-penetrating test. The combination affords the competitive comprehensive performances, including high volumetric and gravimetric energy densities, long cycling life, and superb safety of the LG||Se cell. In addition, with a newly-designed threeelectrode pouch cell, the lithiation of the graphite anodes could be done with an in-situ lithiation process,indicating the high potential of the as-proposed LG||Se cell for the practical applications.

Localized-domains staging structure and evolution in lithiated graphite

Intercalation provides to the host materials a means for controlled variation of many physical/chemical properties and dominates the reactions in metal‐ion batteries.Of particular interest is the graphite intercalation compounds with intriguing staging structures,which however are still unclear,especially in their nanostructure and dynamic transition mechanism.Herein,the nature of the staging structure and evolution of the lithium(Li)‐intercalated graphite was revealed by cryogenic‐transmission electron microscopy and other methods at the nanoscale.The intercalated Li‐ions distribute unevenly,generating local stress and dislocations in the graphitic structure.Each staging compound is found macroscopically ordered but microscopically inhomogeneous,exhibiting a localized‐domains structural model.Our findings uncover the correlation between the long‐range ordered structure and short‐range domains,refresh the insights on the staging structure and transition of Li‐intercalated/deintercalated graphite,and provide effective ways to enhance the reaction kinetic in rechargeable batteries by defect engineering.

In situ tracking of the lithiation and sodiation process of disodium terephthalate as anodes for rechargeable batteries by Raman spectroscopy

Organic compounds represent an appealing group of electrode materials for rechargeable batteries due to their merits of biomass,sustainability,environmental friendliness,and processability.Disodium terephthalate(Na_(2)C_(8)H_(4)O_(4),Na_(2)TP),an organic salt with a theoretical capacity of 255 mAh·g^(-1),is electroactive towards both lithium and sodium.However,its electrochemical energy storage(EES)process has not been directly observed via in situ characterization techniques and the underlying mechanisms are still under debate.Herein,in situ Raman spectroscopy was employed to track the de/lithiation and de/sodiation processes of Na2TP.The appearance and then disappearance of the–COOLi Raman band at 1625 cm^(-1) during the de/lithiation,and the increase and then decrease of the–COONa Raman band at 1615 cm^(-1) during the de/sodiation processes of Na2TP elucidate the one-step with the 2Li+or 2Na+transfer mechanism.We also found that the inferior cycling stability of Na2TP as an anode for sodium-ion batteries(SIBs)than lithium-ion batteries(LIBs)could be due to the larger ion radium of Na+than Li+,which results in larger steric resistance and polarization during EES.The Na2TP,therefore,shows greater changes in spectra during de/sodiation than de/lithiation.We expect that our findings could provide a reference for the rational design of organic compounds for EES.

锂离子电池负极材料银纳米线的锂化机制

为了探究银纳米线在不同工作电压下的锂化机制,借助原位透射电子显微镜的高分辨技术和电子衍射技术,研究了在不同的工作电压条件下,银纳米线在锂化过程中的相变过程和形貌变化。结果表明:金属银用于电池负极材料时,其工作电压对电极材料的活性有较大影响;银在低工作电压下的储锂量大,电极材料不易失效;当工作电压为-1 V时,Ag纳米线在储存锂离子过程中会先变成LiAg相,无明显体积形变;后续随着锂化时间增加,Li_(x)Ag合金中x>1时,纳米线粉碎化,生成Li3Ag、Li9Ag4相;当外加的电压为-2 V时,锂离子会快速在纳米线表面运输并与Ag发生反应,导致纳米线破碎。

二次锂化法制备LiNi_(0.931)Co_(0.049)Al_(0.02)O_(2)单晶正极材料

通过二次锂化技术制备了LiNi_(0.931)Co_(0.049)Al_(0.02)O_(2)单晶NCA正极材料。通过高温预烧结完成Li_(0.96)Ni_(0.95)Co_(0.05)O_(2)材料的制备;随后在预烧结后的物料中补充足够的Al和Li,进行二次烧结制备出NCA单晶正极材料(S2-NCA)。通过本技术制备的高镍单晶正极材料表现出了优异的倍率和循环性能。经过测试,S2-NCA放电比容量可达217.1 mAh/g,60次循环容量保持率可达94.8%,远远优于一次锂化制备的NCA单晶正极材料(S1-NCA),初始比容量为207.9 mAh/g,60次循环容量保持率为85.8%。

正极预锂化添加剂用于锂离子电池的研究进展

锂离子电池因其能量密度高和循环寿命长等优点,在电子产品和电动汽车等领域被广泛应用。然而,锂离子电池首次充放电过程中负极表面固态电解质界面(SEI)膜的形成会永久地消耗正极材料中的活性锂,造成不可逆的容量损失,进而降低电池首次库仑效率。已有的研究表明,预锂化技术可使电池首次库仑效率得到有效提高。在众多预锂化技术中,正极添加剂预锂化具有工艺简单、价格低廉和安全性高等优点,因此具有较为广阔的应用前景。鉴于此,本综述介绍了三类正极预锂化添加剂:三元富锂化合物、二元锂化合物和基于逆转化反应的纳米复合材料的基本工作原理和限制其发展的关键科学问题,着重归纳了近年来在预锂化添加剂材料性能优化,储能机理研究方面的研究进展和亟待解决的问题,指出了补锂添加剂在补偿首次容量损失方面的重要性,并对该方法的发展进行了展望。本文在总结当前研究进展的基础上,对正极预锂化添加剂未来的研究思路和发展方向进行了展望,提出了进一步研究预锂化添加剂的合成条件和改性策略,在不以容量牺牲为代价的前提下提升补锂添加剂的环境稳定性或开发一种新型的电解液添加剂,解决预锂化添加剂首次循环时残留物或产气对电池长循环性能的影响。这些策略有望进一步推动力离子电池的发展。

壳聚糖基自交联粘结剂的合成及其在硅碳负极中的研究

首先以壳聚糖为起始原料,通过羧甲基化处理,显著提升了其水溶性。随后,利用LiOH进行预锂化,并引入双丙酮丙烯酰胺(DAAM)和乙二酸二酰肼(ADH),成功制备了具有出色自交联性能的粘结剂CDD-Li^(+)。为了探究这一粘结剂的结构特性,采用了傅里叶变换红外光谱(FT-IR)技术进行了表征。在粘附性方面,通过180°剥离实验,验证了CDD-Li^(+)的强粘附能力。利用电化学工作站对电池进行了循环伏安曲线的测试。结果显示,CDD-Li^(+)粘结剂所制备的电池能够发生高效的电化学反应,展现出卓越的电化学性能。与常用的聚丙烯酸(PAA)粘结剂相比,CDD-Li^(+)粘结剂在电化学性能上表现更为出色,展现出其在电池领域上的巨大潜力。通过蓝电电池测试仪,进一步研究了电池的倍率性能、循环性能以及锂离子扩散系数,并计算了电池的首圈库伦效率(ICE)。结果显示,CDD-Li^(+)粘结剂制备的电池不仅拥有更优的倍率性能和循环性能,其锂离子扩散系数平均高达10-10数量级,ICE也高达95%。与PAA粘结剂相比,CDD-Li^(+)粘结剂在硅碳负极中展现出更优秀的性能。

锂箔预锂对高比能电池体系性能的影响研究

采用高温热平压工艺将超薄金属锂箔与高比容量硅氧负极进行预锂复合,研究不同预锂量(厚度)对首效的影响;搭配不同高镍正极材料体系,制备单层及10Ah级软包电池进行放大验证,并通过EIS阻抗测试、三电极电位分析和SEM-EDS、SS-NMR表征,研究预锂量(厚度)对首次放电容量和循环性能的影响。结果表明,搭配高镍Ni83与超高镍Ni90三元正极材料体系结果相一致,随着预锂量的增加,首次放电容量和首效明显增加,但循环性能随着预锂量的增加而逐步恶化。5μm锂箔预锂后综合性能提升最优,首效提升至93%,200次循环后容量保持率达到93.4%。双面预锂制备10Ah级软包电池,5μm锂箔预锂的首次充放电效率提升至90%以上,15 W恒功率放电表现出与对照组同等的倍率性能,比能量达到360Wh/kg。

纳米微晶TiO_2合成Li_4Ti_5O_(12)及其嵌锂行为

用溶胶-凝胶法并经热处理制备不同形态和晶体尺寸的TiO2,分别与Li2CO3高温固相反应生成锂钛复合氧化物,经电化学测试发现,用300℃热处理所得纳米微晶TiO2制备的Li4Ti5O12具有良好的嵌锂性能,其可逆比容量大于95 mA·h·g-1,充放电效率近100％,循环性能良好,电压平台平稳,在嵌锂至容量≥85％或脱锂至容量≥90％时均有明显的电压变化,可用作锂离子电池负极材料.

掺杂Li_4Ti_5O_(12)作为锂离子电池负极材料

研究了掺杂元素M (锡、钨、镍 )的锂钛复合氧化物的合成以及Li/掺杂Li4 Ti5O12 实验电池的充放电行为和循环性能。实验结果说明 ,掺杂的Li4 Ti5O12 实验电池其电压平台低于未掺杂的复合氧化物的实验电池 ,电池的首次不可逆容量也小于未掺杂的复合氧化物的Li/Li4 Ti5O12 电池。其中Sn掺杂的Li4 Ti5O12 电极材料循环性能稳定 ,充放电容量较大 ,是一种比较好的锂离子电池的负极材料。

电解液组成对中间相石墨微球电化学性能的影响

以 2 8 0 0℃热处理的煤焦油沥青基中间相石墨微球为锂离子二次电池负极材料 ,考察了中间相石墨微球在不同组成的电解质溶液中的电化学嵌脱锂性能 .确定了试样在不同电解液中电极表面生成的 SEI膜的化学组成和相对含量 ,剖析了共溶剂对 SEI膜形成反应、膜组成和织构的影响 .结果表明 ,在不同共溶剂的 EC基电解液中 ,电极界面 SEI膜形成的电位虽然不同 ,但 SEI膜的化学组成基本相同 ,负极界面 SEI膜的织构是决定电解液与电极材料相容性的关键 .

锂离子电容器集流体用穿孔箔的研究进展

集流体用穿孔箔是锂离子电容器的重要组成部分,不仅为锂离子电容器电极预掺锂提供通道,使锂离子迅速、均匀地掺杂到整个电极中,而且还承载电极活性材料,并将产生的电流汇集起来。系统地介绍了穿孔箔的主要结构参数(孔径、孔隙率)对锂离子电容器电化学性能的影响规律及其机理,并综述了锂离子电容器集流体用穿孔箔的制备方法,最后展望了穿孔箔的发展趋势。

电致变色氧化钨薄膜的干法锂化研究

采用电子束加热蒸发金属Ｌｉ对ＷＯ３电致变色薄膜进行干法锂化，利用Ｘ光电子能谱和电化学方法分析不同锂化程度ＷＯ３薄膜的化学组分和电致变色性能。实验表明，当锂化ＷＯ３薄膜中Ｌｉ原子与Ｗ原子的数目比在０．１５左右时有良好的可逆性和着色效率。利用该方法制备了性能良好的单片式导Ｌｉ＋全固态电致变色薄膜器件Ｇｌａｓｓ／ＩＴＯ／ＷＯ３·Ｌｉ／ＬｉＦ·ＡｌＦ３／Ｖ２Ｏ５／Ａｌ。

锂钛复合氧化物锂离子电池负极材料的研究

采用 3种化学方法合成锂钛复合氧化物 .应用X -射线衍射分析对其结构进行表征以及电化学性能测试 ,结果表明 :由Li2 CO3、TiO2 高温合成的锂钛复合氧化物为尖晶石结构的Li4Ti5 O12 .Li4Ti5 O12 电极在 1 .5V左右有一放电平台 ,充放电可逆性良好 ,即充电电压平台与此接近 ,且电极的比容量较大 ,循环性能良好 .以 0 .30mA·cm- 2 充放电时 ,首次放电容量可达 30 0mAh·g- 1,可逆比容量为 1 0 0mAh·g- 1,经多次充放电循环后 ,其结构仍保持稳定性 .试验电池测试表明 ,Li4Ti5 O12 可选作Li4Ti5 O12 /LiCoO2 锂离子电池的负极材料 .