Probing local electrochemistry via mechanical cyclic voltammetry curves

Tsai, Wan‐Yu; Wang, Ruocun; Boyd, Shelby; Augustyn, Veronica; Balke, Nina

doi:10.1016/j.nanoen.2020.105592

Cited by 30 publications

(32 citation statements)

References 46 publications

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“…To test the hypothesis that cation intercalation into MXene membrane results in swelling of the membrane, we used the operando AFM as a local dilatometer to measure the thickness change of a 16-layer MXene film during cyclic voltammetry (CV) [21] since direct measurement of the nanopore thickness is not feasible. The 16-layer film was deposited by successive repetition of a monolayer MXene self-assembly method we recently developed.…”

Section: Resultsmentioning

confidence: 99%

“…AFM Dilatometry: The experimental and data analysis details of AFM dilatometry were reported elsewhere. [21] In short, the AFM dilatometry was conducted via an MFP-3D AFM in a commercial three-electrode in situ electrochemical AFM cell (both from Asylum Research, Oxford Instruments Company, USA). A 16-layer MXene film was transferred onto a glass carbon substrate as the working electrode.…”

Section: Methodsmentioning

confidence: 99%

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Ionically Active MXene Nanopore Actuators

Mojtabavi

Tsai

VahidMohammadi

et al. 2022

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such as oxygen, hydroxyl, and fluorine bound to the transition metal on the basal plane of the MXenes, and n = 1, 2, 3, or 4. [3] An intriguing property of MXenes (e.g., Ti 3 C 2 T x , Ti 2 CT x , and V 2 CT x ) is that protons and different cations (Li + , Na + , Mg 2+ , etc.) can electrochemically (and chemically) intercalate into the interlayer space between individual MXene flakes. [3] This property has enabled the use of MXenes as electrodes in electrochemical energy storage devices such as batteries [4] and supercapacitors; [5,6] tuning MXene films' electronic, [7] optoelectronic [8] and gas sensing properties; [9] and other exciting applications such as electrochemical actuation. [10,11] In most cases, the improved properties and functionality of MXenes as a result of cation intercalation are due to the accompanying change in their interlayer spacing, as well as charge transfer between the cations and the MXene's outer layer transition metal. [8,9,12] To gain more insights and enable tuning and implementing this property of MXenes for different applications, dynamics of cation intercalation between MXene layers have been extensively studied in the past couple of years. Through using various methods such as electrochemical quartz-crystal admittance (EQCA), [13] electrochemical dilatometry, [14] in situ X-ray diffraction (XRD), [5] and electrochemical atomic force micro scopy (AFM) [10] it was shown that upon intercalation of cations into thick multilayered MXene electrodes (films), a significant and reversible volume change (expansion or contraction based on the cation charge density and size) occurs. [14] However, less attention has been given to ion intercalation Reversible electrochemical intercalation of cations into the interlayer space of 2D materials induces tunable physical and chemical properties in them. In MXenes, a large class of recently developed 2D carbides and nitrides, low intercalation energy, high storage capacitance, and reversible intercalation of various cations have led to their improved performance in sensing and energy storage applications. Herein, a coupled nanopore-actuator system where an ultrathin free-standing MXene film serves as a nanopore support membrane and ionically active actuator is reported. In this system, the contactless MXene membrane in the electric field affects the cation movement in the field through their (de)intercalation between individual MXene flakes. This results in reversible swelling and contraction of the membrane monitored by ionic conductance through the nanopore. This unique nanopore coupled to a mechanical actuation system could provide new insights into designing single-molecule biosensing platforms at the nanoscale.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Ionically Active MXene Nanopore Actuators

Mojtabavi

Tsai

VahidMohammadi

et al. 2022

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“…and Tsai et al. developed the methodology of in situ AFM dilatometry further to probe local redox reactions and charge storage mechanism and introduced the concept of “mechanical” CV (mCV) curves 191,196 . If one assumes that the electrode deformation δ depends linearly on the stored charge Q , then the deformation rate d δ /d t would scale with the electrochemical current I = d Q /d t .…”

Section: Pseudocapacitorsmentioning

confidence: 99%

In situ and operando force‐based atomic force microscopy for probing local functionality in energy storage materials

Gao

Tsai

Balke

2021

Electrochemical Science Adv

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Electrochemical energy storage is the key enabling component of electric vehicles and solar‐/wind‐based energy technologies. The enhancement of energy stored requires the detailed understanding of charge storage mechanisms and local electrochemical and electromechanical phenomena over a variety of length scales from atoms to full cells. Classical electrochemical techniques, such as voltammetry, represent the macroscopic electrochemical properties, and consequently do not allow to extract important information about local electrochemical reactions, ions adsorption, intercalations, and transport. Understanding, controlling, and tuning the local electrochemical functionalities in functional energy materials require in situ/operando techniques which limit the use of structural and functional characterization techniques that provide local information. Here, force‐based atomic force microscopies (AFMs) have provided novel insights into locally probing electrochemical mechanisms on tens of nanometer and even molecular length scales and provide a viable pathway to probe electrochemical processes in situ/operando. In this review, we highlight the contributions in the development and application of force‐based AFM methods to elucidate the local charge storage mechanism in a variety of energy‐related materials. We will focus in particular on methods or AFM modalities in a liquid electrolyte environment.

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“…Figure 1a shows CVs of a vacuum-filtered Ti3C2Tx MXene film in 3 M H2SO4 and three WIS electrolytes, specifically 19.8 m (mol/kg water) lithium chloride (LiCl), 19.2 m lithium bromide (LiBr), and 15 m lithium bis(trifluoromethanesulfonyl)-imide (LiTFSI) aqueous electrolytes. Ti3C2Tx is typically used as a negative electrode material in aqueous systems as Ti3C2Tx is oxidized beyond 0.1-0.2 V vs Ag/AgCl.…”

Section: Activated Electrochemical Processmentioning

confidence: 99%

Titanium carbide MXene shows an electrochemical anomaly in water-in-salt electrolytes

Wang

Mathis

Sun

et al. 2021

Preprint

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Identifying and understanding charge storage mechanisms is important for advancing energy storage, especially when new materials and electrolytes are explored. Well-separated peaks in cyclic voltammograms (CVs) are considered key indicators of diffusion-controlled electrochemical processes with distinct Faradic charge transfer. Herein, we report on an electrochemical system with separated CV peaks, accompanied by surface-controlled partial charge transfer, in 2D Ti3C2Tx MXene in water-in-salt electrolytes. The process involves the insertion/desertion of desolvation-free cations, leading to an abrupt change of the interlayer spacing between MXene sheets. This unusual behavior increases charge storage at positive potentials, thereby increasing the amount of energy stored. This also demonstrates new opportunities for the development of high-rate aqueous energy storage devices and electrochemical actuators using safe and inexpensive aqueous electrolytes.

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Probing local electrochemistry via mechanical cyclic voltammetry curves

Cited by 30 publications

References 46 publications

Ionically Active MXene Nanopore Actuators

Ionically Active MXene Nanopore Actuators

In situ and operando force‐based atomic force microscopy for probing local functionality in energy storage materials

Titanium carbide MXene shows an electrochemical anomaly in water-in-salt electrolytes

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