Nanoscale Morphological Changes at Lithium Interface, Triggered by the Electrolyte Composition and Electrochemical Cycling

Understanding the electrochemical and morphological properties of the Li-electrolyte interface plays a central role in the implementation of metallic Li in safe and efficient electrochemical energy storage. The current study explores the influence of soluble polysulfides (PS) and lithium nitrate (LiNO3) on the characteristics of the solid electrolyte interphase (SEI) layer, formed spontaneously on the Li surface, prior to electrochemical cycling. Special attention is paid to the evolution of the electrochemical impedance and nanoscale morphology of the interface, influenced by the contact time and electrolyte composition. The basic tools applied in this investigation are electrochemical impedance spectroscopy (EIS), atomic force microscopy (AFM) performed at the nanoscale, and X-ray photoelectron spectroscopy (XPS). The individual addition of polysulfides and LiNO3 increases the interface resistance, while the simultaneous application of these components is beneficial, reducing the SEI resistive behavior. The electrochemical cycling of Li in nonmodified 1,2-dimethoxy ethane (DME) and tetraethylene glycol dimethyl ether (TEGDME) based electrolytes leads to slight morphological changes, compared to the pristine Li pattern. In contrast, we found that in the presence of PS and LiNO3, the interface displays a rough and inhomogeneous morphology.

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S-containing and Si-containing compounds as highly effective electrolyte additives for SiOx -based anodes/NCM 811 cathodes in lithium ion cells

Scientific Reports ◽

10.1038/s41598-019-49568-1 ◽

2019 ◽

Vol 9 (1) ◽

Cited By ~ 6

Author(s):

Fuqiang An ◽

Hongliang Zhao ◽

Weinan Zhou ◽

Yonghong Ma ◽

Ping Li

Keyword(s):

Photoelectron Spectroscopy ◽

Elevated Temperatures ◽

Electrochemical Impedance ◽

Solid Electrolyte Interphase ◽

Lithium Ion ◽

Reversible Capacity ◽

High Energy ◽

High Energy Density ◽

Full Cell

Abstract Recently, high-energy density cells containing nickel-rich cathodes and silicon-based anodes have become a practical solution for increasing the driving range of electric vehicles. However, their long-term durability and storage performance is comparatively poor because of the unstable cathode-electrolyte-interphase (CEI) of the high-reactivity cathode and the continuous solid-electrolyte-interphase (SEI) growth. In this work, we study several electrolyte systems consisting of various additives, such as S-containing (1,3,2-dioxathiolane 2,2-dioxide (DTD), DTD + prop-1-ene-1,3-sultone (PES), methylene methanedisulfonate (MMDS)) and Si-containing (tris(trimethylsilyl) phosphate (TTSP) and tris(trimethylsilyl) borate (TMSB)) compounds, in comparison to the baseline electrolyte (BL = 1.0 M LiPF6 + 3:5:2 w-w:w EC: EMC: DEC + 0.5 wt% lithium difluoro(oxalato)borate (LiDFOB) + 2 wt% lithium bis(fluorosulfonyl)imide (LiFSI) + 2 wt% fluoroethylene carbonate (FEC) + 1 wt% 1,3-propane sultone (PS)). Generally, electrolytes with Si-containing additives, particularly BL + 0.5% TTSP, show a lower impedance increase in the full cell, better beginning-of-life (BOL) performance, less reversible capacity loss through long-term cycles and better storage at elevated temperatures than do electrolytes with S-containing additives. On the contrary, electrolytes with S-containing additives exhibit the advantage of low SEI impedance but yield a worse performance in the full cell than do those with Si-containing additives. The difference between two types of additives is attributed to the distinct function of the electrodes, which is characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS), which was performed on full cells and half cells with fresh and harvested electrodes.

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The early-stage growth and reversibility of Li electrodeposition in Br-rich electrolytes

Proceedings of the National Academy of Sciences ◽

10.1073/pnas.2012071118 ◽

2020 ◽

Vol 118 (2) ◽

pp. e2012071118

Author(s):

Prayag Biswal ◽

Atsu Kludze ◽

Joshua Rodrigues ◽

Yue Deng ◽

Taylor Moon ◽

...

Keyword(s):

Photoelectron Spectroscopy ◽

Electrochemical Impedance ◽

Early Stage ◽

Solid Electrolyte Interphase ◽

Growth Dynamics ◽

Ion Diffusion ◽

Reactive Metal ◽

Metal Anode ◽

Sem Image ◽

Fine Control

The physiochemical nature of reactive metal electrodeposits during the early stages of electrodeposition is rarely studied but known to play an important role in determining the electrochemical stability and reversibility of electrochemical cells that utilize reactive metals as anodes. We investigated the early-stage growth dynamics and reversibility of electrodeposited lithium in liquid electrolytes infused with brominated additives. On the basis of equilibrium theories, we hypothesize that by regulating the surface energetics and surface ion/adatom transport characteristics of the interphases formed on Li, Br-rich electrolytes alter the morphology of early-stage Li electrodeposits; enabling late-stage control of growth and high electrode reversibility. A combination of scanning electron microscopy (SEM), image analysis, X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS), and contact angle goniometry are employed to evaluate this hypothesis by examining the physical–chemical features of the material phases formed on Li. We report that it is possible to achieve fine control of the early-stage Li electrodeposit morphology through tuning of surface energetic and ion diffusion properties of interphases formed on Li. This control is shown further to translate to better control of Li electrodeposit morphology and high electrochemical reversibility during deep cycling of the Li metal anode. Our results show that understanding and eliminating morphological and chemical instabilities in the initial stages of Li electroplating via deliberately modifying energetics of the solid electrolyte interphase (SEI) is a feasible approach in realization of deeply cyclable reactive metal batteries.

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Structural changes during the overoxidation of electrochemically deposited poly(3,4-ethylenedioxythiophene) films

Journal of Electrochemical Science and Engineering ◽

10.5599/jese.225 ◽

2016 ◽

Vol 6 (1) ◽

pp. 77 ◽

Cited By ~ 4

Author(s):

Maria Ujvari ◽

Győző G. Láng ◽

Soma Vesztergom ◽

Krisztina J Szekeres ◽

Noémi Kovács ◽

...

Keyword(s):

Structural Changes ◽

Electrochemical Impedance ◽

Morphological Changes ◽

Sodium Sulphate ◽

Film Stress ◽

Morphological Properties ◽

Degree Of Crystallinity ◽

Structure Evolution ◽

Sem Images ◽

Electrode Potentials

Electrochemical, mechanical and morphological properties of thin poly(3,4-ethylenedioxy-thiophene) (PEDOT) films deposited on gold were investigated in aqueous sulfuric acid and sodium sulphate solutions. At sufficiently positive electrode potentials overoxidation of the polymer took place and resulted in morphological changes and structure evolution. These effects were monitored by electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) and X-ray diffraction. Significant changes in the film stress caused by overoxidation were detected by using the electrochemical bending beam method. Results of the EIS measurements proved that the charge transfer process at the metal/film interface is more hindered in case of the degraded film. According to SEM images the overoxidation/degradation of PEDOT films can result in random-like but quite well-ordered arrays of islands and trench-like structures. The diffraction peaks of PEDOT became sharper and more intensive during the subsequent oxidation cycles indicating an increase in the degree of crystallinity of the polymer.

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Influence of VC and FEC Additives on Interphase Properties of Carbon in Li-Ion Cells Investigated by Combined EIS & EQCM-D

10.26434/chemrxiv.12052803.v1 ◽

2020 ◽

Author(s):

Paul Kitz ◽

Matthew Lacey ◽

Petr Novák ◽

Erik Berg

Keyword(s):

Electrochemical Impedance ◽

Solid Electrolyte Interphase ◽

Electrochemical Quartz Crystal Microbalance ◽

Gas Analysis ◽

Side Reactions ◽

Ion Diffusion ◽

Battery Cell ◽

Anode Passivation ◽

Order Of Magnitude ◽

Li Ion

<div>The electrolyte additives vinylene carbonate (VC) and fluoroethylene carbonate (FEC) are well known for increasing the lifetime of a Li-ion battery cell by supporting the formation of an effective solid electrolyte interphase (SEI) at the anode. In this study combined simultaneous electrochemical impedance spectroscopy (EIS) and operando electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) are employed together with in situ gas analysis (OEMS) to study the influence of VC and FEC on the passivation process and the interphase properties at carbon-based anodes. In small quantities both additives reduce the initial interphase mass loading by 30 to 50 %, but only VC also effectively prevents continuous side reactions and improves anode passivation significantly. VC and FEC are both reduced at potentials above 1 V vs. Li+/Li in the first cycle and change the SEI composition which causes an increase of the SEI shear storage modulus by over one order of magnitude in both cases. As a consequence, the ion diffusion coefficient and conductivity in the interphase is also significantly affected. While small quantities of VC in the initial electrolyte increase the SEI conductivity, FEC decomposition products hinder charge transport through the SEI and thus increase overall anode impedance significantly. </div>

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A Facile and Green Synthesis of a MoO2-Reduced Graphene Oxide Aerogel for Energy Storage Devices

Materials ◽

10.3390/ma13030594 ◽

2020 ◽

Vol 13 (3) ◽

pp. 594 ◽

Cited By ~ 3

Author(s):

Mara Serrapede ◽

Marco Fontana ◽

Arnaud Gigot ◽

Marco Armandi ◽

Glenda Biasotto ◽

...

Keyword(s):

Graphene Oxide ◽

Reduced Graphene Oxide ◽

Photoelectron Spectroscopy ◽

Electrochemical Impedance ◽

Chemical Reduction ◽

Low Cost ◽

Xps Analysis ◽

3D Scaffold ◽

Energy Storage Devices ◽

Reduced Graphene

A simple, low cost, and “green” method of hydrothermal synthesis, based on the addition of l-ascorbic acid (l-AA) as a reducing agent, is presented in order to obtain reduced graphene oxide (rGO) and hybrid rGO-MoO2 aerogels for the fabrication of supercapacitors. The resulting high degree of chemical reduction of graphene oxide (GO), confirmed by X-Ray Photoelectron Spectroscopy (XPS) analysis, is shown to produce a better electrical double layer (EDL) capacitance, as shown by cyclic voltammetric (CV) measurements. Moreover, a good reduction yield of the carbonaceous 3D-scaffold seems to be achievable even when the precursor of molybdenum oxide is added to the pristine slurry in order to get the hybrid rGO-MoO2 compound. The pseudocapacitance contribution from the resulting embedded MoO2 microstructures, was then studied by means of CV and electrochemical impedance spectroscopy (EIS). The oxidation state of the molybdenum in the MoO2 particles embedded in the rGO aerogel was deeply studied by means of XPS analysis and valuable information on the electrochemical behavior, according to the involved redox reactions, was obtained. Finally, the increased stability of the aerogels prepared with l-AA, after charge-discharge cycling, was demonstrated and confirmed by means of Field Emission Scanning Electron Microscopy (FESEM) characterization.

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Improvement of Interfacial Adhesion in PP/PS Blends Enhanced with Polyethylene-Polyamine Surface Treated Carbon Fiber

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.1061-1062.170 ◽

2014 ◽

Vol 1061-1062 ◽

pp. 170-174

Author(s):

Jian Li

Keyword(s):

Contact Angle ◽

Carbon Fiber ◽

Photoelectron Spectroscopy ◽

Interfacial Adhesion ◽

Morphological Changes ◽

Water Contact ◽

Polyethylene Polyamine ◽

Adhesion Behavior ◽

Interlaminar Shear ◽

Treated Carbon

The effects of surface treatment of a carbon fiber (CF) by Polyethylene-polyamine (PEPA) on the interfacial adhesion behavior and morphology of polypropylene/polystyrene (PP/PS) matrix blends filled CF composites were investigated. Effects of surface treated a commercial CF on mechanical properties are studied. Contact angle was measured to examine the changes in wettability of the carbon fiber. The chemical and morphological changes were characterized by using X-ray photoelectron spectroscopy (XPS). PP/PS/CF composites were fabricated with and without PEPA treatment, and their interlaminar fracture toughnesses were compared. The results showed that the interlaminar shear strength (ILSS) of composites has been greatly improved filled PEPA modification CF. The water contact angle of resin sample decreased 50% after addition of PEPA surface treated CF.

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Ternary Composite of Molybdenum Disulfide-Graphene Oxide-Polyaniline for Supercapacitor

Journal of The Electrochemical Society ◽

10.1149/1945-7111/ac3f1e ◽

2021 ◽

Author(s):

Ke Qu ◽

Yuqi Bai ◽

Miao Deng

Keyword(s):

Graphene Oxide ◽

Molybdenum Disulfide ◽

Photoelectron Spectroscopy ◽

Electrochemical Impedance ◽

Light Emitting Diode ◽

Rate Capability ◽

Energy Storage And Conversion ◽

Carbon Paper ◽

Power Sources ◽

X Ray

Abstract The ever-increasing need for small and lightweight power sources for use in portable or wearable electronic devices has spurred the development of supercapacitors as a promising energy storage and conversion system. In this work, a simple, facile and easy-to-practice method has been developed to employ carbon paper (CP) as the support to coat molybdenum disulfide (MoS2) and graphene oxide (GO), followed by electrodeposition of polyaniline (PANI) to render CP/MoS2-GO-PANI. The preparation parameters, such as amounts of MoS2, GO and number of aniline electropolymerization cycles, have been optimized to render CP/MoS2-GO-PANI the best capacitive performance. The as-prepared optimal CP/MoS2-GO-PANI is characterized by X-ray powder diffraction, scanning electron microscopy, energy-dispersive spectroscopy, and X-ray photoelectron spectroscopy. The supercapacitive properties of CP/MoS2-GO-PANI as an electrode have been evaluated electrochemically via cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy testing. CP/MoS2-GO-PANI delivers a specific capacitance of 255.1 F/g at 1.0 A/g and exhibits excellent rate capability under larger current densities. Moreover, a symmetrical supercapacitor is assembled and three are connected in series to power a light-emitting diode for ~15 minutes, demonstrating the promising application potential of CP/MoS2-GO-PANI-based supercapacitor.

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The electrocatalytic response of metallophthalocyanines when clicked to electrodes and to nanomaterials

10.21504/10962/172191 ◽

2021 ◽

Author(s):

◽

Lekhetho Simon Mpeta

Keyword(s):

Hydrogen Peroxide ◽

Silver Nanoparticles ◽

Zinc Oxide ◽

Photoelectron Spectroscopy ◽

Electrocatalytic Activity ◽

Electrochemical Impedance ◽

Modified Electrodes ◽

Transmission Electron ◽

Reduced Graphene ◽

Electrochemical Microscopy

Conjugates of nanomaterials and metallophthalocyanines (MPcs) have been prepared and their electrocatalytic activity studied. The prepared nanomaterials are zinc oxide and silver nanoparticles, reduced graphene oxide nanosheets and semiconductor quantum dots. The MPcs used in this work are cobalt (II) (1a), manganese(III) (1b) and iron (II) (1c) 2,9(10),16(17),23(24)- tetrakis 4-((4-ethynylbenzyl) oxy) phthalocyaninato, 2,9(10),16(17),23(24)- tetrakis(5-pentyn-oxy) cobalt (II) phthalocyaninato (2), 9(10),16(17),23(24)- tris-[4-tert-butylphenoxy)-2- (4-ethylbezyl-oxy) cobalt (II) phthalocyaninato (3), 9(10),16(17),23(24)- tris-[4-tertbutylphenoxy)-2-(pent-4yn-yloxy)] cobalt (II) phthalocyaninato (4), cobalt (II) (5a) and manganese (III) (5b) 2,9(10),16(17),23(24)- tetrakis [4-(4-(5-chloro-1H-benzo [d]imidazol-2-yl)phenoxy] phthalocyaninato and 9(10),16(17),23(24)- tris tert butyl phenoxy- 2- [4-(4-(5-chloro-1H-benzo[d]imidazole-2-yl)phenoxy] cobalt (II) phthalocyaninato (6). Some of these MPcs (1a, 3 and 4) were directly clicked on azide grafted electrode, while some (1b, 1c, 2, 5a and 5b) were clicked to azide functionalised nanomaterials and then drop-dried on the electrodes. One phthalocyanine (5b) was drop-dried on the electrode then silver nanoparticles were electrodeposited on it taking advantage of metal-N bond. Scanning electrochemical microscopy, voltammetry, chronoamperometry, electrochemical impedance spectroscopy are among electrochemical methods used to characterise modified electrodes. Transmission electron microscopy, X-ray photoelectron spectroscopy, Xray diffractometry, Raman spectroscopy and infrared spectroscopy were employed to study surface functionalities, morphology and topography of the nanomaterials and complexes. Electrocatalytic activity of the developed materials were studied towards oxidation of 2-mercaptoethanol, hydrazine and hydrogen peroxide while the reduction study was based on oxygen and hydrogen peroxide. In general, the conjugates displayed superior catalytic activity when compared to individual materials. Complex 2 alone and when conjugated to zinc oxide nanoparticles were studied for their nonlinear optical behaviour. And the same materials were explored for their hydrazine detection capability. The aim of this study was to develop sensitive, selective and affordable sensors for selected organic waste pollutants. Conjugates were found to achieve the aim of the study compared to when individual materials were employed.

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One-step chemical vapor deposition synthesis and supercapacitor performance of nitrogen-doped porous carbon–carbon nanotube hybrids

Beilstein Journal of Nanotechnology ◽

10.3762/bjnano.8.267 ◽

2017 ◽

Vol 8 ◽

pp. 2669-2679 ◽

Cited By ~ 14

Author(s):

Egor V Lobiak ◽

Lyubov G Bulusheva ◽

Ekaterina O Fedorovskaya ◽

Yury V Shubin ◽

Pavel E Plyusnin ◽

...

Keyword(s):

Chemical Vapor Deposition ◽

Hybrid Materials ◽

Vapor Deposition ◽

Porous Carbon ◽

Photoelectron Spectroscopy ◽

Electrochemical Impedance ◽

Chemical Vapor ◽

Carbon Surface ◽

Simultaneous Formation ◽

Nitrogen Doped

Novel nitrogen-doped carbon hybrid materials consisting of multiwalled nanotubes and porous graphitic layers have been produced by chemical vapor deposition over magnesium-oxide-supported metal catalysts. CN x nanotubes were grown on Co/Mo, Ni/Mo, or Fe/Mo alloy nanoparticles, and MgO grains served as a template for the porous carbon. The simultaneous formation of morphologically different carbon structures was due to the slow activation of catalysts for the nanotube growth in a carbon-containing gas environment. An analysis of the obtained products by means of transmission electron microscopy, thermogravimetry and X-ray photoelectron spectroscopy methods revealed that the catalyst's composition influences the nanotube/porous carbon ratio and concentration of incorporated nitrogen. The hybrid materials were tested as electrodes in a 1M H2SO4 electrolyte and the best performance was found for a nitrogen-enriched material produced using the Fe/Mo catalyst. From the electrochemical impedance spectroscopy data, it was concluded that the nitrogen doping reduces the resistance at the carbon surface/electrolyte interface and the nanotubes permeating the porous carbon provide fast charge transport in the cell.

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Organosilane-functionalization of nanostructured indium tin oxide films

Interface Focus ◽

10.1098/rsfs.2016.0056 ◽

2016 ◽

Vol 6 (6) ◽

pp. 20160056 ◽

Cited By ~ 10

Author(s):

R. Pruna ◽

F. Palacio ◽

M. Martínez ◽

O. Blázquez ◽

S. Hernández ◽

...

Keyword(s):

Surface Area ◽

Indium Tin Oxide ◽

Photoelectron Spectroscopy ◽

Electrochemical Impedance ◽

Annealing Treatment ◽

Electrochemical Analysis ◽

Cyclic Voltammograms ◽

X Ray ◽

Chip Technology ◽

Significant Difference

Fabrication and organosilane-functionalization and characterization of nanostructured ITO electrodes are reported. Nanostructured ITO electrodes were obtained by electron beam evaporation, and a subsequent annealing treatment was selectively performed to modify their crystalline state. An increase in geometrical surface area in comparison with thin-film electrodes area was observed by atomic force microscopy, implying higher electroactive surface area for nanostructured ITO electrodes and thus higher detection levels. To investigate the increase in detectability, chemical organosilane-functionalization of nanostructured ITO electrodes was performed. The formation of 3-glycidoxypropyltrimethoxysilane (GOPTS) layers was detected by X-ray photoelectron spectroscopy. As an indirect method to confirm the presence of organosilane molecules on the ITO substrates, cyclic voltammetry and electrochemical impedance spectroscopy (EIS) were also carried out. Cyclic voltammograms of functionalized ITO electrodes presented lower reduction-oxidation peak currents compared with non-functionalized ITO electrodes. These results demonstrate the presence of the epoxysilane coating on the ITO surface. EIS showed that organosilane-functionalized electrodes present higher polarization resistance, acting as an electronic barrier for the electron transfer between the conductive solution and the ITO electrode. The results of these electrochemical measurements, together with the significant difference in the X-ray spectra between bare ITO and organosilane-functionalized ITO substrates, may point to a new exploitable oxide-based nanostructured material for biosensing applications. As a first step towards sensing, rapid functionalization of such substrates and their application to electrochemical analysis is tested in this work. Interestingly, oxide-based materials are highly integrable with the silicon chip technology, which would permit the easy adaptation of such sensors into lab-on-a-chip configurations, providing benefits such as reduced size and weight to facilitate on-chip integration, and leading to low-cost mass production of microanalysis systems.

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