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Electrochemical SPM investigation of the solid electrolyte interphase film formed on HOPG electrodes
《Electrochemistry communications》2000,2(6):436-440
Solid electrolyte interphase (SEI) film formation on graphite electrodes was studied on highly oriented pyrolytic graphite (HOPG) in nonaqueous electrolyte by in situ electrochemical atomic force microscopy (AFM). For potentials negative to 0.7 V versus Li|Li+ a SEI film is formed on the HOPG electrode surface. After the first cycle the film is rough and covers the surface of the HOPG electrode only partially. After the second cycle the HOPG surface is fully covered by a compact film. The thickness of the SEI film was measured by increasing the pressure of the AFM tip and thus scraping a part of the electrode surface. In this way a thickness of about 25 nm was found for the SEI film formed after two scan cycles between 3 and 0.01 V versus Li|Li+. 相似文献
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丁磺酸内酯对锂离子电池性能及负极界面的影响 总被引:5,自引:0,他引:5
用循环伏安(CV)、电化学阻抗谱(EIS)、扫描电镜(SEM)、能谱分析(EDS)及理论计算等方法研究了添加剂丁磺酸内酯(BS)对锂离子电池负极界面性质的影响. 研究表明, 在初次循环过程中, BS具有较低的最低空轨道能量, 优先于溶剂在石墨电极上还原分解, 并形成固体电解质相界面膜(SEI膜). 在含BS的电解液中形成的SEI膜的热稳定性高, 在70 ℃下储存24 h后, 膜电阻和电荷迁移电阻大小基本保持不变, 而在不含BS的电解液中形成的SEI膜的热稳定性较差, 在70 ℃下储存24 h后, 膜电阻和电荷迁移电阻大小有明显的增加. 从BS对锂离子电池电化学性能影响的研究表明, 加入少量的BS能够显著提高锂离子电池的室温放电容量、低温及高温储存放电性能. 相似文献
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Shah Rahim Alam Naveed A. Razzaq Amir Cheng YANG Yujie CHEN Jiapeng HU Xiaohui ZHAO Yang PENG Zhao DENG 《物理化学学报》2019,35(12):1382-1390
As an important component in electrodes, the choice of an appropriate binder is significant when fabricating lithium-ion batteries (LIBs) with good cycle stability and rate capability, which are used in numerous applications, especially portable electronics and eco-friendly electric vehicles (EVs). Semi-crystalline poly(vinylidene fluoride) (PVDF), which is a traditional and widely used binder, cannot efficiently accommodate the volume changes observed in the anode during the charge-discharge process while binding all the components in the electrode together, which results in increased internal cell resistance, detachment of the electrode components, and capacity fading. Herein, we have investigated a highly polar and elastomeric polyacrylonitrile-butadiene (NBR) rubber for use as a binder in LIBs, which can accommodate graphite particles of different shapes compared to semi-crystalline PVDF. Prior to our electrochemical tests, NBR was analyzed using thermogravimetric analysis (TGA) and X-ray diffraction (XRD), showing good thermal stability and an amorphous morphology. NBR is more conformable to irregular surfaces, which results in the formation of a homogeneous passivation layer on both spherical and flaky graphite particles to effectively suppress any electrolyte side reactions, further allowing more uniform and fast Li ion diffusion at the electrolyte/electrolyte interface. As a result, the electrochemical performance of both spherical and flaky shape graphite electrodes was significantly improved in terms of their first cycle Coulombic efficiency (CE) and cycle stability. With comparative specific capacity, the first cycle CE of the NBR-based spherical and flaky graphite electrodes were 87.0% and 85.5%, compared to 85.3% and 82.6% observed for their corresponding PVDF-based electrodes, respectively. After 1000 discharge-charge cycles at 1C, the capacity retention of the NBR-based graphite electrodes was significantly higher than that of PVDF-based electrodes. This was attributed to the good stability of the solid electrolyte interphase (SEI) formed on the graphite electrodes and the high stretching ability of the elastomeric NBR binder, which help to accommodate the repeated volume fluctuation of graphite observed during long-term charge-discharge cycling. Electrochemical impedance spectroscopy (EIS) and microscopic analysis (SEM and TEM) were carried out to investigate the formation and evolution of the SEI layers formed on the spherical and flaky graphite electrodes. The results show that thin, homogeneous, and stable SEI layers are formed on the surface of both spherical and flaky graphite electrodes prepared using the NBR binder. When compared to the PVDF-based graphite electrodes, the graphite electrodes constructed using NBR showed decreased resistance in the SEI layer and faster charge transfer, thus enhancing the electrode kinetics for Li ion intercalation/deintercalation. Our study shows that the electrochemical performance of spherical and flaky graphite electrodes prepared using the NBR binder is significantly improved, demonstrating that NBR is a promising binder for these electrodes in LIBs. 相似文献
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We investigate the formation and distribution of the solid electrolyte interface (SEI) layer on a graphite anode with two additives [vinylethylene carbonate (VEC) and vinylene carbonate (VC)] in a formation process using XPS, field emission AES, and extreme high‐resolution SEM (XHR‐SEM) techniques, and we studied what factors play an important role in determining the formation of the SEI layer. The VEC‐derived SEI behaviors (morphology, thickness, compound, and balance over electrode position) on a graphite anode largely depend on the elevated temperature. The VC‐derived SEI layer is mostly formed in the initial charging step, showing simple growth (formation) behavior. It is suggested that the properties of the additives are important for SEI bonding configurations at the nanoscale film surface, and to achieve the stable SEI layer, there appears to be an effective formation process for the additive properties. This research highlights the challenges of developing a stable SEI layer with additives in the formation process for electric vehicle batteries and would make a contribution to the understanding of how formation conditions affect an SEI layer with respect to additive properties. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
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温度对石墨电极性能的影响 总被引:1,自引:0,他引:1
运用电化学阻抗谱(EIS)并结合循环伏安法(CV)研究了石墨电极25和60 ℃时在1 mol·L-1 LiPF6-EC(碳酸乙烯酯):DEC(碳酸二乙酯):DMC(碳酸二甲酯)电解液中, 以及60 ℃时在1 mol·L-1 LiPF6-EC:DEC:DMC+5%VC(碳酸亚乙烯酯)电解液中的首次阴极极化过程. 发现高温下(60 ℃)石墨电极在1 mol·L-1 LiPF6-EC:DEC:DMC电解液中可逆循环容量衰减的主要原因在于其表面无法形成稳定的固体电解质相界面(SEI)膜. 实验结果显示, VC添加剂能够增进高温下石墨电极表面SEI膜的稳定性, 进而改进石墨电极的循环性能. 相似文献
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通过循环伏安(CV)、电化学阻抗谱(EIS)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)和傅立叶变换红外(FTIR)光谱研究了双乙二酸硼酸锂(LiBOB)基电解液在石墨表面的成膜性及其在常温(25 ℃)和高温(70 ℃)下对石墨循环性能的影响. 结果表明, LiBOB基电解液的成膜电位在1.7 V, 其中BOB-离子还原形成的草酸盐是固体电解质相界面(SEI)膜的有效成分之一. 电化学阻抗谱显示, 膜阻抗在循环过程中呈现减小趋势, 这有利于提高循环稳定性. 在常温和高温条件下, 石墨在该电解液体系中均表现出优于其在LiPF6基电解液体系中的循环性能. 相似文献
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In this paper, we fabricated 1.7 A h soft-packed cells using commercial-grade LiFePO4 and manmade graphite as the active materials for the cathode and anode, respectively. It has been shown that the cycle performances of assembled soft-packed full-cell were still temperature-dependent. An accelerated mechanism of the operating temperature to reformation/repairing of SEI layer have been established, which greatly consumes active lithium during cycling, therefore causes fast capacity loss at elevated temperatures. At same time, cycle property for LiFePO4/graphite cell with different depth of discharge (DOD) levels and ranges. It has been shown that DOD level has very little effect on capacity fade for cell lifecycle; but for DOD range, obvious influence was observed on capacity fade, which is due to the sensitivity of SOC during the storage of the cell. 相似文献
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Transition metal selenides have been widely studied as anode materials of sodium ion batteries(SIBs),however,the investigation of solid-electrolyte-interface(SEI)on these materials,which is critical to the electrochemical performance of SIBs,remains at its infancy.Here in this paper,ZnSe@C nanoparticles were prepared from ZIF-8 and the SEI layers on these electrodes with and without reduced graphene oxide(rGO)layers were examined in details by X-ray photoelectron spectroscopies at varied charged/discharged states.It is observed that fast and complicated electrolyte decomposition reactions on ZnSe@C leads to quite thick SEI film and intercalation of solvated sodium ions through such thick SEI film results in slow ion diffusion kinetics and unstable electrode structure.However,the presence of rGO could efficiently suppress the decomposition of electrolyte,thus thin and stable SEI film was formed.ZnSe@C electrodes wrapped by rGO demonstrates enhanced interfacial charge transfer kinetics and high electrochemical performance,a capacity retention of 96.4%,after 1000 cycles at 5 A/g.This study might offer a simple avenue for the designing high performance anode materials through manipulation of SEI film. 相似文献
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This article critically evaluates the characteristics of a new in situ spectroelectrochemical cell with an optimized path
of the IR beam, designed in our laboratory for study of the solid electrolyte interphase (SEI) layer formed between a porous
graphite anode and alkyl carbonate solution for lithium-ion batteries. The cell was designed in view of the optical principles
underlying the way the in situ cell works, to give depth of penetration of the evanescent IR beam through the attenuated total
internal reflectance crystal into the electrolyte at such a small value, ranging from 0.277 to 2.77 μm, that it was possible
to minimize the "masking effect" of the ethylene carbonate/diethyl carbonate solvent. Moreover, the "local compositional change"
which may arise significantly from the "thin layer electrolyte configuration" cell also could be fairly avoided, since only
the electrolyte in the vicinity of the electrode composed of graphite particles is reduced to form the SEI layer to a thickness
of at most 0.1 μm during the application of potentials. Thus, it was possible to measure the in situ FT-IR spectra in the
cell, which represents the real chemical composition and structure of the SEI layer. Taking the application of the designed
in situ cell as an example, this article reports the effect of salt type and electrolyte temperature on the chemical composition
and structure of the SEI layer between graphite particles and alkyl carbonate solution with the help of various measured in
situ FT-IR spectra.
Electronic Publication 相似文献
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《Surface and interface analysis : SIA》2005,37(10):773-781
The formation of a passivation film (solid electrolyte interphase, SEI) at the surface of the negative electrode of full LiCoO2/graphite lithium‐ion cells using LiPF6 (1M ) in carbonate solvents as electrolyte was investigated by means of x‐ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The analyses were carried out at different potentials of the first and the fifth cycles, showing the potential‐dependent character of the surface‐film species formation. These species were mainly identified as Li2CO3 up to 3.8 V and LiF up to 4.2 V. This study shows the formation of the SEI during charging and its partial dissolution during discharge. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
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Yan Cheng Guan Wang Manming Yan Zhiyu Jiang 《Journal of Solid State Electrochemistry》2007,11(2):310-316
The interfacial properties of mesocarbon-microbeads (MCMB) and lithium electrodes during charge process in poly (vinylidenefluoride-co-hexafluoropropylene)-based gel electrolyte were investigated by in situ Raman microscopy, in situ Fourier transform-infrared (FTIR) spectroscopic methods, and charge–discharge, electrochemical impedance spectroscopy techniques. For MCMB electrode, the series phase transitions from initial formation of the dilute stage 1 graphite intercalation compound (GIC) to a stage 4 GIC, then through a stage 3 to stage 2, and finally to stage 1 GIC was proved by in situ Raman spectroscopic measurement. The formation of solid electrolyte interface (SEI) films formed on MCMB and metal lithium electrode was studied by in situ reflectance FTIR spectroscopic method. At MCMB electrode surface, the solvent (mostly ethylene carbonate) decomposed during charging process and ROCO2Li may be the product. ROCO2Li, ROLi, and Li2CO3 were the main composites of SEI film formed on lithium electrode, not on electrodeposited lithium electrode or lithium foil electrode. 相似文献
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V. S. Kolosnitsyn E. V. Kuz’mina E. V. Karaseva S. E. Mochalov 《Russian Journal of Electrochemistry》2011,47(7):793-798
Changes in the properties of lithium-sulfur cells during cycling were studied by impedance spectroscopy. The electric conductivity
of the electrolyte changed during the charging and discharging of the lithium-sulfur cells as a result of the dissolution
of lithium polysulfides formed in electrochemical reactions. The maximum resistance of the electrolyte and the surface layers
on the sulfur and lithium electrodes was achieved in the region of the transition between the low- and high-voltage areas
on the charge and discharge curves of the cells. This region corresponded to the highest concentration of lithium polysulfides
in the electrolyte. For nearly charged or discharged lithium-sulfur cells, the impedance spectra contained linear segments
which could be attributed to diffusion limitations at low frequencies. An analysis of the results of impedance studies suggested
that the electrochemical processes in lithium-sulfur cells were controlled by diffusion in the surface layer on the sulfur
electrode at high degrees of charge or discharge and by the transport properties of the electrolytic system at moderate degrees
of charging. 相似文献
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二氟二草酸硼酸锂对LiFePO4/石墨电池高温性能的影响 总被引:2,自引:0,他引:2
研究了二氟二草酸硼酸锂(LiODFB)作为锂盐加入到碳酸丙烯酯(PC)+碳酸乙烯酯(EC)+碳酸甲乙酯(EMC)(质量比为1:1:3)混合溶剂中对LiFePO4/石墨电池高温(60 ℃)循环性能的影响. 用线性扫描伏安法(LSV)测试了电解液的电化学窗口. 通过等离子发射光谱(ICP)和能量散射光谱(EDS)对LiFePO4材料高温条件下在不同电解液中的稳定性进行了研究; 并用扫描电镜(SEM)和电化学交流阻抗谱(EIS)分析了石墨负极表面的固体电解液相界面(SEI)膜的热稳定性. 结果表明: 一方面LiODFB基电解液能抑制LiFePO4材料在高温条件下Fe(II)的溶解, 防止溶解的Fe(II)在石墨上还原, 有效地降低电池阻抗; 另一方面, 在LiODFB基电解液中形成的石墨负极表面SEI膜具有更好的热稳定性, 能显著提高LiFePO4/石墨电池的高温循环性能. 相似文献
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The effect of solid electrolyte interface formation conditions on the aging performance of Li-ion cells 总被引:1,自引:0,他引:1
Chenghuan Huang Kelong Huang Haiyan Wang Suqin Liu Yuqun Zeng 《Journal of Solid State Electrochemistry》2011,15(9):1987-1995
The effect of formation temperatures and current densities on the aging performance of LiNi1/3Co1/3Mn1/3O2/artificial graphite Li-ion cells during storage and cycle was investigated using three-electrode electrochemical impedance
spectroscopy and charge–discharge experiment. The higher formation temperature at 45 °C decreased the resistance of solid
electrolyte interphase (SEI) film and the irreversible capacity loss of Li-ion cells during SEI formation process. After Li-ion
cell storage at 60 °C for 10 weeks, the ohmic resistance of the negative electrodes and the irreversible capacity loss of
the cells reduced 24% and 7.9%, respectively, accompanied by a significant decrease of SEI film resistance when the formation
temperature increased from 25 to 45 °C. The higher temperature at 45 °C may facilitate the transformation of metastable ROCO2Li to stable inorganics to form a stable SEI film. Three hundred cycling tests indicated that the capacity retention of the
cell formation at 25 °C was only 87.5%, about 8% less than that of the cell formation at 45 °C. However, the SEI formation
current density did not significantly affect the property of SEI film and the irreversible capacity loss of the aged cells. 相似文献
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I. V. Krylova L. N. Ivanov V. E. Bozhevol’nov A. V. Severin 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2007,81(2):241-245
Low-temperature (20–360°C) exoemission of negative charges from nanocrystalline hydroxyapatite Ca10(PO4)6(OH)2 was studied. Thermal cycling and storage at 20°C were found to induce self-organization processes with charge separation and the formation of a negatively charged layer on the surface. The negative charge formed was long retained at elevated temperatures and only decreased during cooling in the temperature region of the structural transition, as is characteristic of thermoelectrets. No stable electrets formed in hydroxyapatite samples calcined at a high temperature (>800°C). 相似文献