Electrochemical quartz crystal microbalance measurement of a Li4Ti5O12 composite electrode in a carbonate electrolyte

Serizawa, Nobuyuki; Shono, Kumi; Kobayashi, Yo; Miyashiro, Hajime; Katayama, Yasushi; Miura, Takashi

doi:10.1016/j.jpowsour.2015.06.148

Cited by 5 publications

(4 citation statements)

References 27 publications

(29 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, the Sauerbrey equation always needs a correction related to the electrode/electrolyte interface. Another factor that affects the frequency shift is the change of density (ρ L ) and viscosity (η L ) of the electrolyte in contact with the quartz crystal electrode, , as follows …”

Section: Methodsmentioning

confidence: 99%

“…From eq , we see that Δ f ηρ has a negative linear correlation with Δ R . However, due to the inhomogeneous concentration of the electrolyte near the electrode during the charge–discharge process (including density and viscosity, η L ρ L ), Δ R is also affected by roughness of the electrode, which changes when strong deposition reaction occurs, such as electrolyte decomposition at <2.6 V region . It is difficult to arrive at an accurate quantitative relationship between Δ R and Δ f ηρ .…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Revealing of the Activation Pathway and Cathode Electrolyte Interphase Evolution of Li-Rich 0.5Li₂MnO₃·0.5LiNi_0.3Co_0.3Mn_0.4O₂ Cathode by in Situ Electrochemical Quartz Crystal Microbalance

Yin

Peng

et al. 2019

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

1The first-cycle behavior of layered Li-rich oxides, including Li 2 MnO 3 activation and cathode 2 electrolyte interphase (CEI) formation, significantly influences their electrochemical performance. 3 However, the Li 2 MnO 3 activation pathway and the CEI formation process are still controversial. 4 Here, the first-cycle properties of xLi 2 MnO 3 •(1-x) LiNi 0.3 Co 0.3 Mn 0.4 O 2 (x = 0, 0.5, 1) cathode 5 materials were studied with an in-situ electrochemical quartz crystal microbalance (EQCM). The 6 results demonstrate that a synergistic effect between layered Li 2 MnO 3 and LiNi 0.3 Co 0.3 Mn 0.4 O 2 7structures can significantly affect the activation pathway of Li 1.2 Ni 0.12 Co 0.12 Mn 0.56 O 2 , leading to an 8 extra-high capacity. It is demonstrated that Li 2 MnO 3 activation in Li-rich materials is dominated by 9 electrochemical decomposition (oxygen redox), which is different from the activation process of pure 10 Li 2 MnO 3 governed by chemical decomposition (Li 2 O evolution). CEI evolution is closely related to 11 Li + extraction/insertion. The valence state variation of the metal ions (Ni, Co, Mn) in Li-rich material 12 can promote CEI formation. This study is of significance for understanding and designing Li-rich 13 cathode-based batteries. 15Continuing interest in sustainable use of Li-ion batteries (LIBs) for electrical transportation is 2 driving further developments in cathode materials. Layered Li-rich oxide cathode materials exhibit 3 high specific capacity of more than 250 mAh g -1 and thus are considered as potential candidates for 4 the next-generation LIBs. 1-2 Nevertheless, commercial applications of Li-rich cathode materials are 5 hindered by three main drawbacks. First, a large irreversible capacity loss happens in the first 6 charge-discharge process. Second, their cyclability and rate capability are not sufficient. Third, 7 significant voltage decay occurs during cycling. [3][4][5] All these issues are highly related to the first-cycle 8 charge-discharge processes. Therefore, a better understanding and further controlling of the 9 first-cycle processes of the Li-rich oxide cathode will be beneficial to improve its electrochemical 10 properties. 11Li 2 MnO 3 activation and cathode electrolyte interphases (CEI) formation/dissolution are two key 12 reactions of Li-rich oxides in the first cycle. Many previous studies have been done to understand the 13 activation process of Li 2 MnO 3 and CEI evolution. However, there is no consensus on the Li 2 MnO 3 14 activation process. 6-11 For example, it was claimed that O 2− was oxidized to an O 2 2− species or 15 O 2 2− -like localized electron holes on oxygen ("oxygen redox") during Li 2 MO 3 (M =Ru, Sn, Mn) 16 activation . [6][7][8][9] In contrast, other studies show very different Li 2 O evolution processes. 10-11 So far, 17 most results were achieved using ex-situ electron paramagnetic resonance (EPR), X-ray 18 photoelectron spectroscopy (XPS), 6 resonant inelastic X-ray scattering (RIXS), 7 in-situ Raman, [9][10] 19 and wavelength...

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Revealing of the Activation Pathway and Cathode Electrolyte Interphase Evolution of Li-Rich 0.5Li₂MnO₃·0.5LiNi_0.3Co_0.3Mn_0.4O₂ Cathode by in Situ Electrochemical Quartz Crystal Microbalance

Yin

Peng

et al. 2019

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

show abstract

“…[50][51][52][53] Serizawa et al studied in detail the resonance resistance change during Li-insertion and extraction operations of Li4Ti5O12-coated EQCM electrodes. 54 The stability of Li4Ti5O12 materials that experience no volumetric or surface morphological alterations enabled to quantitatively detect both the changes in electrode mass and physical properties of the surrounding electrolyte during electrochemical operation. However, in the case of Li metal electrode reactions, EQCM analyses are difficult to apply.…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, the physical information of the electrolytes, such as viscosity or elasticity, cannot be directly accessed. The electrochemical quartz-crystal microbalance (EQCM) technique is a well-known sensing technique to identify the mass change of electrodes during various electrochemical reactions, such as corrosion, plating, surface film formation, , electrode dissolution, and Li metal deposition. − Additionally, the resonance resistance ( R res ) of oscillations is closely related to viscosity (η) and mass density (ρ) of electrode surface compounds and the surrounding electrolyte. − Serizawa et al studied in detail the resonance resistance change during Li-insertion and extraction operations of Li 4 Ti 5 O 12 -coated EQCM electrodes . The stability of Li 4 Ti 5 O 12 materials that experience no volumetric or surface morphological alterations enabled to quantitatively detect both the changes in electrode mass and physical properties of the surrounding electrolyte during electrochemical operation.…”

Section: Introductionmentioning

confidence: 99%

In-Operando Detection of the Physical Property Changes of an Interfacial Electrolyte during the Li-Metal Electrode Reaction by Atomic Force Microscopy

Kitta

2020

Langmuir

View full text Add to dashboard Cite

This manuscript propose the operando detection technique of the physical properties change of electrolyte during Li-metal battery operation.The physical properties of electrolyte solution such as viscosity (η) and mass densities (ρ) highly affect the feature of electrochemical Li-metal deposition on the Li-metal electrode surface.Therefore, the operando technique for detection these properties change near the electrode surface is highly needed to investigate the true reaction of Li-metal electrode. Here, this study proved that one of the atomic force microscopy based analysis, energy dissipation analysis of cantilever during force curve motion, was really promising for the direct investigation of that. The solution drag of electrolyte, which is controlled by the physical properties, is directly concern the energy dissipation of cantilever motion. In the experiment, increasing the energy dissipation was really observed during the Li-metal dissolution (discharge) reaction, understanding as the increment of η and ρ of electrolyte via increasing of Li-ion concentration. Further, the dissipation energy change was well synchronized to the charge-discharge reaction of Li-metal electrode.This study is the first report for direct observation of the physical properties change of electrolyte on Li-metal electrode reaction, and proposed technique should be widely interesting to the basic interfacial electrochemistry, fundamental researches of solid-liquid interface, as well as the battery researches. File list (2)download file view on ChemRxiv Manscript for ChemRxiv.pdf (0.90 MiB) download file view on ChemRxiv Supporting Information for ChemRxiv.pdf (353.90 KiB)

show abstract

In situanalytical techniques for battery interface analysis

2018

View full text Add to dashboard Cite

Lithium-ion batteries, simply known as lithium batteries, are distinct among high energy density charge-storage devices. The power delivery of batteries depends upon the electrochemical performances and the stability of the electrode, electrolytes and their interface. Interfacial phenomena of the electrode/electrolyte involve lithium dendrite formation, electrolyte degradation and gas evolution, and a semi-solid protective layer formation at the electrode-electrolyte interface, also known as the solid-electrolyte interface (SEI). The SEI protects electrodes from further exfoliation or corrosion and suppresses lithium dendrite formation, which are crucial needs for enhancing the cell performance. This review covers the compositional, structural and morphological aspects of SEI, both artificially and naturally formed, and metallic dendrites using in situ/in operando cells and various in situ analytical tools. Critical challenges and the historical legacy in the development of in situ/in operando electrochemical cells with some reports on state-of-the-art progress are particularly highlighted. The present compilation pinpoints the emerging research opportunities in advancing this field and concludes on the future directions and strategies for in situ/in operando analysis.

show abstract

Electrochemical quartz crystal microbalance measurement of a Li4Ti5O12 composite electrode in a carbonate electrolyte

Cited by 5 publications

References 27 publications

Revealing of the Activation Pathway and Cathode Electrolyte Interphase Evolution of Li-Rich 0.5Li₂MnO₃·0.5LiNi_0.3Co_0.3Mn_0.4O₂ Cathode by in Situ Electrochemical Quartz Crystal Microbalance

Revealing of the Activation Pathway and Cathode Electrolyte Interphase Evolution of Li-Rich 0.5Li₂MnO₃·0.5LiNi_0.3Co_0.3Mn_0.4O₂ Cathode by in Situ Electrochemical Quartz Crystal Microbalance

In-Operando Detection of the Physical Property Changes of an Interfacial Electrolyte during the Li-Metal Electrode Reaction by Atomic Force Microscopy

In situanalytical techniques for battery interface analysis

Contact Info

Product

Resources

About

Electrochemical quartz crystal microbalance measurement of a Li4Ti5O12 composite electrode in a carbonate electrolyte

Cited by 5 publications

References 27 publications

Revealing of the Activation Pathway and Cathode Electrolyte Interphase Evolution of Li-Rich 0.5Li2MnO3·0.5LiNi0.3Co0.3Mn0.4O2 Cathode by in Situ Electrochemical Quartz Crystal Microbalance

Revealing of the Activation Pathway and Cathode Electrolyte Interphase Evolution of Li-Rich 0.5Li2MnO3·0.5LiNi0.3Co0.3Mn0.4O2 Cathode by in Situ Electrochemical Quartz Crystal Microbalance

In-Operando Detection of the Physical Property Changes of an Interfacial Electrolyte during the Li-Metal Electrode Reaction by Atomic Force Microscopy

In situanalytical techniques for battery interface analysis

Contact Info

Product

Resources

About

Revealing of the Activation Pathway and Cathode Electrolyte Interphase Evolution of Li-Rich 0.5Li₂MnO₃·0.5LiNi_0.3Co_0.3Mn_0.4O₂ Cathode by in Situ Electrochemical Quartz Crystal Microbalance

Revealing of the Activation Pathway and Cathode Electrolyte Interphase Evolution of Li-Rich 0.5Li₂MnO₃·0.5LiNi_0.3Co_0.3Mn_0.4O₂ Cathode by in Situ Electrochemical Quartz Crystal Microbalance