Novel in situ and ex situ techniques for the study of lithium/electrolyte interfaces

Zhuang, Guorong; Wang, Kuilong; Chottiner, Gary S.; Barbour, R. L.; Luo, Yuyan; Bae, In Tae; Tryk, Donald A.; Scherson, Daniel Alberto

doi:10.1016/0378-7753(94)02034-z

Cited by 13 publications

(6 citation statements)

References 8 publications

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“…The last 15 years has seen FTIR ATR widely used in the in situ investigation of adsorption from aqueous solution. − The main focus of this research has been adsorption from solution directly onto the IRE, onto a thin film coated onto the IRE, or onto a finely dispersed solid making good contact with the IRE. Silicon, , germanium, , and KRS-5 15,16 IREs have been regularly used as adsorbates themselves (other materials have also been utilized), and IRE coatings have included elemental silicon 18 and gold, alumina, polymers, and biopolymers . Of particular interest to us has been the growing volume of literature concerning adsorption from aqueous media onto finely dispersed solids.…”

Section: Introductionmentioning

confidence: 99%

“…The main focus of this research has been adsorption from solution directly onto the IRE, onto a thin film coated onto the IRE, or onto a finely dispersed solid making good contact with the IRE. Silicon, 11,12 germanium, 13,14 and KRS-5 15,16 IREs have been regularly used as adsorbates themselves (other materials have also been utilized), 17 and IRE coatings have included elemental silicon 18 and gold, 19 alumina, 20 polymers, 21 and biopolymers. 22 Of particular interest to us has been the growing volume of literature concerning adsorption from aqueous media onto finely dispersed solids.…”

Section: Introductionmentioning

confidence: 99%

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Attenuated Total Reflection Fourier Transform Infrared Spectroscopic Investigation of the Solid/Aqueous Interface of Low Surface Area, Water-Soluble Solids in High Ionic Strength, Highly Alkaline, Aqueous Media

1997

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A new method for the investigation of the adsorption of the series of surface active quaternary ammonium (QA) compounds, dodecyltrimethylammonium bromide (C12), tetradecyltrimethylammonium bromide (C14), and hexadecyltrimethylammonium bromide (C16) on the surface of sodium oxalatesa Bayer process solidshas been developed using Fourier transform infrared (FTIR) attenuated total reflection (ATR) spectroscopy. The technique involves the use of a finely ground sodium oxalate combined with an appropriate adsorption matrix and, for the first time, permits the in situ investigation of adsorption from high ionic strength, highly alkaline (pH 12), aqueous media onto a water soluble, low surface area solid: sodium oxalate (a compound traditionally treated as ligand or adsorbate). Spectroscopic results show the formation of surfactant aggregate clusters on the surface of sodium oxalate and suggest adsorption in the order C16 > C14 > C12. This new method will allow the acquisition of "dose-response" curves for the C12, C14, and C16 QAs on sodium oxalate (under the aforementioned conditions), while also leading to the in situ investigation of the surface of sodium oxalate in synthetic and process Bayer liquors (high ionic strength, extremely alkaline media). Our results suggest that this method will be well suited to interfacial research in other similar areas involving complex, nonideal industrial systems which also depend upon chemical processes occurring at the solid/aqueous and solid/liquid interfaces.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Attenuated Total Reflection Fourier Transform Infrared Spectroscopic Investigation of the Solid/Aqueous Interface of Low Surface Area, Water-Soluble Solids in High Ionic Strength, Highly Alkaline, Aqueous Media

1997

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“…[20,21] Scherson et al successfully detected reaction products and anions on sputtered Au thin-film electrodes in SPEs (poly(ethylene oxide) [PEO]-LiClO 4 electrolyte). [22,23] In this work, operando ATR-IR and ex situ XPS techniques coupled with linear sweep voltammetry and EIS were used to understand the surface (electro)chemical process of PEO 10 lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) electrolyte during the lithium secondary battery operation. A sputtered Cu electrode was selected as a model negative electrode due to its high chemical stability against Li, simplifying the investigation of the surface (electro)chemical process.…”

Section: Introductionmentioning

confidence: 99%

“…[ 20,21 ] Scherson et al successfully detected reaction products and anions on sputtered Au thin‐film electrodes in SPEs (poly(ethylene oxide) [PEO]‐LiClO 4 electrolyte). [ 22,23 ]…”

Section: Introductionmentioning

confidence: 99%

(Electro)Chemical Processes of Poly(Ethylene Oxide)‐Based Electrolyte on Cu Surface during Lithium Secondary Battery Operation

2023

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Understanding the surface electrochemistry of polymer electrolytes under battery operating conditions is of great importance for tuning the solid electrolyte interphase (SEI) in lithium batteries with polymer electrolytes. Herein, the surface (electro)chemical process of poly(ethylene oxide) (PEO) lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) (PEO10LiTFSA) electrolyte on the Cu electrode is studied by operando attenuated total reflection infrared (ATR‐IR) and ex situ X‐ray photoelectron spectroscopy (XPS) techniques coupled with the interfacial resistance obtained from electrochemical impedance spectroscopy (EIS). Linear sweep voltammogram of the Cu electrode in PEO10LiTFSA electrolyte suggests the SEI‐like layer formation involves three reduction steps. Operando ATR‐IR, ex situ XPS, and EIS reveal the corresponding (electro)chemical processes and their effect on the interfacial resistance; LiTFSA and residual H2O and CO2 are first reduced, forming an inorganic SEI‐like layer without affecting the interfacial resistance. Subsequently, the PEO matrix reduces into several decomposed products, including CC components, responsible for the most resistive SEI‐like layer. Finally, PEO‐decomposed species with CC components further reduce into alkyl‐related species, leading significant reduction of the resistance of the SEI‐like layer. The study successfully reveals the complex surface (electro)chemical process at the PEO electrolyte–Cu electrode interface, and may serve as a model system for understanding SEI component and interfacial resistance relationship in the polymer electrolyte system.

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“…0022-3654/95/2099-11797$09.00/0 attenuated total reflection Fourier transform infrared (ATR-Fi'lk) spectroscopy, a series of spectroelectrochemical measurements were performed under reduced pressure, on the order of a fraction of a pascal. 4 Such an approach did, as desired, decrease the effects associated with gas-phase contaminants, without modifying the overall electrochemical response. Prompted by the possibility of conducting such experiments under even lower pressures, we investigated the degassing properties of ultrapurified PEO, LiC104, and, later, LiC104/PE0 films, using a turbomolecular pump and ultimately an ion-pumped chamber equipped with a mass spectrometer.…”

Section: Introductionmentioning

confidence: 99%

Electrochemistry in Ultrahigh Vacuum: Intercalation of Lithium into the Basal Plane of Highly Oriented Pyrolytic Graphite from a Poly(ethylene oxide)/LiClO4 Solid Polymer Electrolyte

Gofer¹,

Barbour²,

Luo³

et al. 1995

J. Phys. Chem.

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The electrochemical insertion of lithium into the basal plane of highly ordered pyrolytic graphite (HOPG-(bp)) from a LiClOdPEO solid polymer electrolyte has been examined in ultrahigh vacuum (UHV) using a carefully designed electrochemical cell. On the basis of a comparison of the data obtained with those recorded for the same interfacial system in an inert gas at atmospheric pressure, it has been concluded that the electrochemical behavior observed in UHV is indeed characteristic of the Li/L,iClO4(PEO)/HOPG(bp) system and therefore not affected in any discernible way by the ultralow pressures. Coulometric analysis of cyclic voltammetry experiments showed that the charge associated with lithium intercalation is larger than that observed during subsequent deintercalation, particularly during the first few intercalation-deintercalation cycles. However, the total amount of impurities observed in Auger electron spectra of emersed HOPG(bp) surfaces following lithium intercalation was very low. This last finding is inconsistent with the presence of a film of any significant thickness on the surface, suggesting that the charge imbalance for this interface is due to kinetic hindrances during lithium deintercalation. IntroductionThe advent of solid polymeric materials displaying high ionic mobilities at relatively low temperatures has opened new prospects for improved electrical energy-storage and energygeneration devices.' Battery technology has been focused on solid organic polymers capable of transporting lithium ions but impervious to attack by metallic lithium.* Highly promising is poly(ethy1ene oxide) (PEO),3 a material that shows moderate Li+-ion conductivities at temperatures as low as 55 "C even in the absence of cosolvents or other additives.During in situ characterization of the short-term stability of ultrapurified PEO-based electrolytes toward metallic Li using

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Novel in situ and ex situ techniques for the study of lithium/electrolyte interfaces

Cited by 13 publications

References 8 publications

Attenuated Total Reflection Fourier Transform Infrared Spectroscopic Investigation of the Solid/Aqueous Interface of Low Surface Area, Water-Soluble Solids in High Ionic Strength, Highly Alkaline, Aqueous Media

Attenuated Total Reflection Fourier Transform Infrared Spectroscopic Investigation of the Solid/Aqueous Interface of Low Surface Area, Water-Soluble Solids in High Ionic Strength, Highly Alkaline, Aqueous Media

(Electro)Chemical Processes of Poly(Ethylene Oxide)‐Based Electrolyte on Cu Surface during Lithium Secondary Battery Operation

Electrochemistry in Ultrahigh Vacuum: Intercalation of Lithium into the Basal Plane of Highly Oriented Pyrolytic Graphite from a Poly(ethylene oxide)/LiClO4 Solid Polymer Electrolyte

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