Hierarchical Storage Behavior of Tetrafluoroborate Anion in Graphite Electrodes

Li, Jiayu; Wang, Xiaohong; Wang, Yunju; Kamezaki, Hisamitsu; Yoshio, Masaki

doi:10.1149/2.0201912jes

Cited by 12 publications

(21 citation statements)

References 45 publications

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“…The intercalation of BF 4 − ions in an AC/graphite capacitor results in a thickness change of up to 8.25% (see Figure 7 ). [28a] Both publications proved that capacitive and pseudocapacitive processes can be distinguished using ECD in combination with CV.…”

Section: Ecd For Electrochemical Energy Storage Devicesmentioning

confidence: 97%

“…Only very small thickness changes are expected as long as only ion adsorption takes place [8i,8k,8l,27] . Additional pseudocapacitive or intercalation processes lead to larger expansion [8b,8d,8l,28] . Note that ECD research studies on supercapacitors typically use voltage sweep measurements (linear sweep voltammetry [LSV], cyclic voltammetry [CV]) rather than constant current measurements that are more popular in battery research.…”

Section: Ecd For Electrochemical Energy Storage Devicesmentioning

confidence: 99%

“…Change in electrode thickness (here named “height change”) versus voltage changes of a graphite/AC supercapacitor with SBPBF 4 in propylene carbonate as electrolyte (SBP = spiro‐(1,1′)‐bipyrrolidinium). Reproduced with permission [28a] . Copyright 2019, The Electrochemical Society.…”

Section: Ecd For Electrochemical Energy Storage Devicesmentioning

confidence: 99%

“…However, the process of SEI formation also involves the formation of gases that might influence the thickness of the electrode (see Chapter 4 for gas evolution). Other explanations for the large irreversible change may be exfoliation, [8b,20h,31] changes of the active material, [8a,11c,22c] swelling due to the electrolyte, [22c] irreversible trapping of ions inside the structure, [28b] or a more loose particle network [8h,13b,32] …”

Section: Evaluation Of Ecd Data Analysis and Interpretation Of The Datamentioning

confidence: 99%

“…This can be explained by differences of the ion size. Herein, not the bare ion size has to be taken into account as the size of the unsolvated ion does not correlate with the measured thickness change [8i,28d] . Thus, the solvation of the ion might play an important role [8b,8i] .…”

Section: Evaluation Of Ecd Data Analysis and Interpretation Of The Datamentioning

confidence: 99%

See 4 more Smart Citations

A Practical Guide for Using Electrochemical Dilatometry as Operando Tool in Battery and Supercapacitor Research

Escher

Hahn²,

Ferrero

et al. 2022

Energy Tech

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Lithium‐ion batteries and related battery concepts show an expansion and shrinkage (“breathing”) of the electrodes during cell cycling. The dimensional changes of an individual electrode or a complete cell can be continuously measured by electrochemical dilatometry (ECD). The obtained data provides information on the electrode/cell reaction itself but can be also used to study side reactions or other relevant aspects, e.g., how the breathing is influenced by the electrode binder and porosity. The method spans over a wide measurement range and allows the determination of macroscopic as well as nanoscopic changes. It has also been applied to supercapacitors. The method has been developed already in the 1970s but recent advancements and the availability of commercial setups have led to an increasing interest in ECD. At the same time, there is no “best practice” on how to evaluate the data and several pitfalls exist that can complicate the comparison of literature data. This review highlights the recent development and future trends of ECD and its use in battery and supercapacitor research. A practical guide on how to evaluate the data is provided along with a discussion on various factors that influence the measurement results.

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Section: Ecd For Electrochemical Energy Storage Devicesmentioning

confidence: 97%

Section: Ecd For Electrochemical Energy Storage Devicesmentioning

confidence: 99%

Section: Ecd For Electrochemical Energy Storage Devicesmentioning

confidence: 99%

Section: Evaluation Of Ecd Data Analysis and Interpretation Of The Datamentioning

confidence: 99%

Section: Evaluation Of Ecd Data Analysis and Interpretation Of The Datamentioning

confidence: 99%

See 3 more Smart Citations

A Practical Guide for Using Electrochemical Dilatometry as Operando Tool in Battery and Supercapacitor Research

Escher

Hahn²,

Ferrero

et al. 2022

Energy Tech

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Difluoro(oxalato)borate's Role in the Intercalation Behavior of Mixed Anions from Sulfolane

Wang

2022

ChemSusChem

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Some previous studies have found the synergistic effect of mixed anions in dual‐ion batteries (DIBs). In this work, both lithium tetrafluoroborate (LiBF4) and lithium difluoro(oxalato)borate (LiDFOB) were dissolved in sulfolane (SL) solvent, and the resultant solutions were applied for DIBs. The storage behavior of mixed anions in natural graphite positive electrodes was investigated. In‐situ X‐ray diffraction measurements revealed both anions could participate in the formation of graphite intercalation compounds. Their evolution followed with the decreasing tendency of discharge capacities as the content of LiDFOB increased in solutions. The exchange of anions was discussed.

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Electrochemical intercalation of anions into graphite: Fundamental aspects, material synthesis, and application to the cathode of dual‐ion batteries

Matsuo,

Inoo,

Inamoto

2024

ChemistryOpen

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In this review, fundamental aspects of the electrochemical intercalation of anions into graphite have been first summarized, and then described the electrochemical preparation of covalent‐type GICs and application of graphite as the cathode of dual‐ion battery. Electrochemical overoxidation of anion GICs provides graphite oxide and covalent‐fluorine GICs, which are key functional materials for various applications including energy storage devices. The reaction conditions to obtain fully oxidized graphite has been mentioned. Concerning the application of graphite for the cathode of dual‐ion battery, it stably delivers about 110 mA h g−1 of reversible capacity in usual organic electrolyte solutions. The combination of anion and solvent as well as the concentration of the anions in the electrolyte solutions greatly affect the performance of graphite cathode such as oxidation potential, rate capability, cycling properties, etc. The interfacial phenomenon is also important, and fundamental studies of charge transfer resistance, anion diffusion coefficient, and surface film formation behavior have also been summarized. The use of smaller anions, such as AlCl4−, Br− can increase the capacity of graphite cathode. Several efforts on the structural modification of graphite and development of electrolyte solutions in which graphite cathode delivers higher capacity were also described.

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Hierarchical Storage Behavior of Tetrafluoroborate Anion in Graphite Electrodes

Cited by 12 publications

References 45 publications

A Practical Guide for Using Electrochemical Dilatometry as Operando Tool in Battery and Supercapacitor Research

A Practical Guide for Using Electrochemical Dilatometry as Operando Tool in Battery and Supercapacitor Research

Difluoro(oxalato)borate's Role in the Intercalation Behavior of Mixed Anions from Sulfolane

Electrochemical intercalation of anions into graphite: Fundamental aspects, material synthesis, and application to the cathode of dual‐ion batteries

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