Netanel Shpigel, Mikhael D Levi, Sergey Sigalov, Doron Aurbach, Leonid Daikhin and Volker Presser 1 Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel 2 School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences, Tel-Aviv University, Ramat Aviv 69978, Israel 3 INM—Leibniz Institute for New Materials, 66123 Saarbrücken, Germany 4 Department of Materials Science and Engineering, Saarland University, 66123 Saarbrücken, Germany

The high phase-transformation strain developed upon intercalation in the host particles of a composite battery electrode affects the polymeric binder network mechanically, deteriorating the electrode cycling performance Here, electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) is used to demonstrate a new strain-accommodation mechanism, in high-strain NaFePO4/PVdF electrodes, via relaxation of the binder network surrounding the intercalation particles. Complete mechanical degradation of the polymer network occurs during long-term cycling of NaFePO4 electrodes in aqueous solutions (hard and tough behavior). In contrast, in aprotic solutions, a softened binder easily accommodates the high transformation strain, ensuring excellent electrode cycling performance (soft and tough behavior). Quantification of the high-frequency viscoelastic properties of an operating composite electrode linked to the binder's fracture toughness ensures fast and facile screening of the optimal polymeric binder/electrolyte solution combinations. This methodology should be extremely important for optimization of cycling performance of Li-Si anodes undergoing huge volume changes during cycling,

Quartz crystal microbalance with dissipation monitoring (QCM-D) generates surface-acoustic waves in quartz crystal plates that can effectively probe the structure of films, particulate composite electrodes of complex geometry rigidly attached to quartz crystal surface on one side and contacting a gas or liquid phase on the other side. The output QCM-D characteristics consist of the resonance frequency (MHz frequency range) and resonance bandwidth measured with extra-ordinary precision of a few tenths of Hz. Depending on the electrodes stiffness/softness, QCM-D operates either as a gravimetric or complex mechanical probe of their intrinsic structure. For at least 20 years, QCM-D has been successfully used in biochemical and environmental science and technology for its ability to probe the structure of soft solvated interfaces. Practical battery and supercapacitor electrodes appear frequently as porous solids with their stiffness changing due to interactions with electrolyte solutions or as a result of ion intercalation/adsorption and long-term electrode cycling. Unfortunately, most QCM measurements with electrochemical systems are carried out based on a single (fundamental) frequency and, as such, provided that the resonance bandwidth remains constant, are suitable for only gravimetric sensing. The multiharmonic measurements have been carried out mainly on conducting/redox polymer films rather than on typical composite battery/supercapacitor electrodes. Here, we summarize the most recent publications devoted to the development of electrochemical QCM-D (EQCM-D)-based methodology for systematic characterization of mechanical properties of operating battery/supercapacitor electrodes. By varying the electrodes' composition and structure (thin/thick layers, small/large particles, binders with different mechanical properties, etc.), nature of the electrolyte solutions and charging/cycling conditions, the method is shown to be operated in different application modes. A variety of useful electrode-material properties are assessed noninvasively, in situ, and in real time frames of ion intercalation into the electrodes of interest. A detailed algorithm for the mechanical characterization of battery electrodes kept in the gas phase and immersed into the electrolyte solutions has been developed for fast recognition of stiff and viscoelastic materials in terms of EQCM-D signatures treated by the hydrodynamic and viscoelastic models. Working examples of the use of in situ hydrodynamic spectroscopy to characterize stiff rough/porous solids of complex geometry and viscoelastic characterization of soft electrodes are presented. The most demonstrative example relates to the formation of solid electrolyte interphase on Li4Ti5O12 electrodes in the presence of different electrolyte solutions and additives: only a few cycles (an experiment during ∼30 min) were required for screening the electrolyte systems for their ability to form high-quality surface films in experimental EQCM-D cells as compared to 100 cycles (200 h cycling) in conventional coin cells. Thin/small-mass electrodes required for the EQCM-D analysis enable accelerated cycling tests for ultrafast mechanical characterization of these electrodes in different electrolyte solutions. Hence, this methodology can be easily implemented as a highly effective in situ analytical tool in the field of energy storage and conversion.

Electrophoretically deposited (EPD) lithium ferrophosphate (LFP) electrodes (LiFePO4) containing either soft Mg(OH)2 or rigid PVdF binders have been fabricated and tested in Li2SO4 aqueous solution. The use of Electrochemical Quartz-Crystal Microbalance with dissipation monitoring (EQCM-D) was shown to be extremely advantageous to distinguish between the effectively viscoelastic and rigid states of LFP and LFP/PVdF electrodes, respectively, based already on the raw EQCM-D (i.e. recording resonant frequency and resonance width changes of the electrode on multiple overtone orders). The approach that we developed for testing composite battery and supercapacitor electrodes is quite general, and includes mechanical characterizations of the electrodes in air, in contact with liquids and electrolyte solutions, and most importantly, during combined electrochemical and mechanical characterization of battery electrodes subjected to Li-ions insertion/extraction. A new theory of hydrodynamic admittance of porous semispherical bumps has been developed and successfully applied for the characterization of rigid porous LFP/PVdF composite electrode in its both intercalated and deintercalated states. We show that the extended Voight-type viscoelastic model describes quantitatively the intercalated and deintercalated states of LFP electrode coating containing soft Mg(OH)2 binder. The approach based on non-gravimetric application of EQCM-D developed in this work is unique and quite promising for in-situ mechanical characterization of a large variety of battery and supercapacitor electrodes for energy-storage devices.

It is generally accepted that solid–electrolyte interphase formed on the surface of lithium-battery electrodes play a key role in controlling their cycling performance. Although a large variety of surface-sensitive spectroscopies and microscopies were used for their characterization, the focus was on surface species nature rather than on the mechanical properties of the surface films. Here we report a highly sensitive method of gravimetric and viscoelastic probing of the formation of surface films on composite Li 4 Ti 5 O 12 electrode coupled with lithium ions intercalation into this electrode. Electrochemical quartz-crystal microbalance with dissipation monitoring measurements were performed with LiTFSI, LiPF 6 , and LiPF 6 + 2% vinylene carbonate solutions from which structural parameters of the surface films were returned by fitting to a multilayer viscoelastic model. Only a few fast cycles are required to qualify surface films on Li 4 Ti 5 O 12 anode improving in the sequence LiPF 6 < LiPF 6 + 2% vinylene carbonate << LiTFSI.

Intercalation-induced dimensional changes of composite battery electrodes containing either a stiff or a soft polymeric binder is one of the many factors determining the cycling performance and ageing. Herein, we report dimensional changes in bulk composite electrodes by in situ electrochemical dilatometry (eD) combined with electrochemical quartz-crystal microbalance with dissipation monitoring (EQCM-D). The latter tracks the mechanical properties on the level of the electrode particle size. Lithium iron phosphate (LiFePO4, LFP) electrodes with a stiff binder (PVdF) and a soft binder (NaCMC) were investigated by cycling in lithium sulfate (Li2SO4) aqueous solution. The electrochemical and mechanical electrode performances depend on the electrode cycling history. Based on combined eD and EQCM-D measurements we provide evidence which properties are preferred for a binder used for a composite Li-ion battery electrode.

Viscoelastic properties of battery electrodes in contact with electrolyte solutions may affect the electrodes' cycling performance. However, they are not easily assessed by in situ measurements. Herein, we show that an electrochemical quartz-crystal microbalance with dissipation (EQCM-D) enables extraordinary sensitive probing of intrinsic electrodes materials' properties such as intercalation induced gravimetric and viscoelastic changes, using Ti3C2(OH)(2) (MXene) as a classical 2D intercalation model material. The insertion of each Li-ion into thin electrodes comprising this MXene is accompanied by insertion of one water molecule. Solvent-dependent viscoelastic changes and periodic stiffening/softening upon fully reversible Li-ion intercalation/deintercalation into an MXene electrode correlates well with its excellent long-term cycling performance. The experimental platform based on a commercial instrument, EQCM-D monitoring, and Voight-type modeling (extended Voight-type model) can be used for in situ real time characterization of intrinsic materials' properties of practical composite battery electrodes important for a deeper understanding of the factors controlling their cycling performance.

Intercalation-induced dimensional changes in a composite battery electrode (comprising a polymeric binder) are one of the major factors limiting electrode cycling performance. Since electrode performance is expressed by the quantities averaged over its entire surface area (e.g., capacity retention, Faradaic efficiency, rate capability), significant efforts have been made to develop a methodology allowing its facile mechanical diagnostics at the same areal scale. Herein we introduce such a generic methodology for a highly sensitive in situ monitoring of intrinsic mechanical properties of composite battery electrodes. The gravimetric, dimensional, viscoelastic, and adhesive changes in the composite electrodes caused by Li-ions intercalation are assessed noninvasively and in real time by electrochemical quartz-crystal microbalance with dissipation monitoring (EQCM-D). Multiharmonic acoustic waves generated by EQCM-D penetrate into thin porous electrodes comprising either rigid or a soft binder resulting in frequency and dissipation changes quantified by analytical acoustic load impedance models. As a first demonstration, we used a composite LiFePO4 (LFP) electrode containing either polyvinylidene dichloride (PVdF) or Na carboximethyl cellulose (NaCMC) as rigid and viscoelastic binders, respectively, in aqueous electrolytes. The intercalation-induced volume changes of LFP electrode were evaluated from a hydrodynamic correction to the mass effect of the intercalated ions for PVdF, and both components of the effective complex shear modulus (i.e., storage and loss moduli) in case of NaCMC binder have been extracted. The sliding friction coefficients for large particles bound at their bottom to the quartz crystal surface (a measure of the adhesion strength of binders) has also been evaluated. Tracking the mechanical properties of the composite electrodes in different environments and charging/cycling conditions in a self-consistent manner provides all necessary conditions for an optimal selection of the polymeric binders resistant to intercalation-induced volume changes of intercalation particles.

A great advantage of non-gravimetric vs. conventional gravimetric mode of quartz-crystal microbalance (QCM) has been demonstrated for quantification of the hydrodynamic interactions of rigid porous electrode coatings with contacting electrolyte solutions. The complex frequency change of these electrodes measured by multiharmonic EQCM-D (Electrochemical QCM with Dissipation Monitoring) contains implicit information about the initial porous electrode structure at open-circuit potential and its minute changes caused by Li-ions intercalation into the electrode host. Fitting suitable hydrodynamic models to the experimental complex frequency changes allows determination of the initial geometric parameters of the porous electrode in contact with solution as well as their potential-dependent changes. Validation of structural parameters derived by the hydrodynamic models for a large number of porous structure geometries using penetration depth as a unique mesoscopic independent variable should be done using complementary techniques with different resolution power. A meaningful application of EQCM-D in Li-ion batteries R&D is only possible under strict control over numerous contributions to the total complex frequency change from the processes accompanying intercalation of ions into the electrode (viscoelastic effects of binders, formation of surface-electrolyte interface, side reactions with gas evolution, etc.)

Using multiharmonic electrochemical quartz crystal microbalance with dissipation (EQCM-D) monitoring, a new method of characterization of porous solids in contact with liquids has been developed. The dynamic gravimetric information on the growing, dissolving, or stationary stored solid deposits is supplemented by their precise in-operando porous structure characterization on a mesoscopic scale. We present a very powerful method of quartz-crystal admittance modeling of hydrodynamic solid-liquid interactions in order to extract the porous structure parameters of solids during their formation in real time, using different deposition modes. The unique hydrodynamic spectroscopic characterization of electrolytic and rf-sputtered solid Cu coatings that we use for our "proof of concept" provides a new strategy for probing various electrochemically active thin and thick solid deposits, thereby offering inexpensive, noninvasive, and highly efficient quantitative control over their properties. A broad spectrum of applications of our method is proposed, from various metal electroplating and finishing technologies to deeper insight into dynamic build-up and subsequent development of solid-electrolyte interfaces in the operation of Li-battery electrodes, as well as monitoring hydrodynamic consequences of metal corrosion, and growth of biomass coatings (biofouling) on different solid surfaces in seawater.

Herein the application of a recently introduced new method of tracking in-situ the intercalation-induced deformations of supercapacitor and Li-battery electrodes is reviewed. The method is based on the use of multi-harmonic electrochemical quartz microbalance with dissipation monitoring, EQCM-D (in-situ hydrodynamic spectroscopy) which enables a permanent control of the electrodes' state-of-health by probing their mechanical properties. The potential-dependent frequency and resonance width changes are fitted to a chosen hydrodynamic admittance model allowing thus quantification of the electrode deformations under different charging conditions. Intercalation of different alkaline metal cations into layered MXene electrode serves as a readily understandable working example of quantifying such electrodes deformations. Further method developments including in-situ viscoelastic characterization of composite porous electrodes are envisaged in the near future.

A primary atomic-scale effect accompanying Li-ion insertion into rechargeable battery electrodes is a significant intercalation-induced change of the unit cell volume of the crystalline material. This generates a variety of secondary multiscale dimensional changes and causes a deterioration in the energy storage performance stability. Although traditional in situ height-sensing techniques (atomic force microscopy or electrochemical dilatometry) are able to sense electrode thickness changes at a nanometre scale, they are much less informative concerning intercalation-induced changes of the porous electrode structure at a mesoscopic scale. Based on a electrochemical quartz-crystal microbalance with dissipation monitoring on multiple overtone orders, herein we introduce an in situ hydrodynamic spectroscopic method for porous electrode structure characterization. This new method will enable future developments and applications in the fields of battery and supercapacitor research, especially for diagnostics of viscoelastic properties of binders for composite electrodes and probing the micromechanical stability of their internal electrode porous structure and interfaces.

Multiharmonic analysis by electrochemical quartz-crystal microbalance with dissipation monitoring (EQCM-D) is introduced as an excellent tool for quantitative studying electrosorption of ions from aqueous solution in mesoporous (BP-880) or mixed micro-mesoporous (BP-2000) carbon electrodes. Finding the optimal conditions for gravimetric analysis of the ionic content in the charged carbon electrodes, we propose a novel approach to modeling the charge-dependent gravimetric characteristics by incorporation of Gouy-Chapman-Stern electric double layer model for ions electrosorption into meso- and micro-mesoporous carbon electrodes. All three parameters of the gravimetric equation evaluated by fitting it to the experimental mass changes curves were validated using supplementary nitrogen gas sorption analysis and complementing atomic force microscopy. Important overlap between gravimetric EQCM-D analysis of the ionic content of porous carbon electrodes and the classical capacitive deionization models has been established. The necessity and usefulness of non-gravimetric EQCM-D characterizations of complex carbon architectures, providing insight into their unique viscoelastic behavior and porous structure changes, have been discussed in detail.

Reversible Li-ion intercalation into composite Li-ion battery (LIB) electrodes is often accompanied by significant dimensional electrode changes (deformation) resulting in significant deterioration of the cycling performance. Viscoelastic properties of polymeric binders affected by intercalation-induced deformation of composite LIB electrodes have never been probed in situ on operating electrochemical cells. Here, we introduce a newly developed noninvasive method, namely electrochemical quartz-crystal microbalance with dissipation monitoring (EQCM-D), for in situ monitoring of elastic properties of polymeric binders during charging of LIB electrodes. As such, we find EQCM-D as a uniquely suitable tool to track the binder's structural rigidity/softness in composite Li insertion electrodes in real-time by the characteristic increase/decrease of the dissipation factor during the charging-discharging process. The binders partially swollen in aprotic solutions demonstrate intermediate viscoelastic charge-rate-dependent behavior, revealing rigid/soft behavior at high/low charging rates, respectively. The method can be adjusted for continuous monitoring of elastic properties of the polymeric binders over the entire LIB electrodes cycling life.

Fast ion adsorption processes in supercapacitors enable quick storage/delivery of significant amounts of energy, while ion intercalation in battery materials leads to even larger amounts of energy stored, but at substantially lower rates due to diffusional limitations. Intercalation of ions into the recently discovered 2D Ti3C2Tx (MXene) occurs with a very high rate and leads to high capacitance, posing a paradox. Herein, by characterizing the mechanical deformations of MXene electrode materials at various states‐of‐charge with a variety of cations (Li, Na, K, Cs, Mg, Ca, Ba, and three tetra­alkylammonium cations) during cycling by electrochemical quartz‐crystal admittance (EQCA, quartz‐crystal microbalance with dissipation monitoring) combined with in situ electronic conductance and electrochemical impedance, light is shone on this paradox. Based on this work, it appears that the capacitive paradox stems from cationic insertion, accompanied by significant deformation of the MXene particles, that occurs so rapidly so as to resemble 2D ion adsorption at solid‐liquid interfaces. The latter is greatly facilitated by the presence of water molecules between the MXene sheets.

This paper describes the application of Electrochemical Quartz Crystal Admittance (EQCA) methodology to the tracking of ion adsorption on composite electrode coatings consisting of highly porous activated carbon particles and polyvinylidene difluoride (PVdF) binder rigidly attached to quartz crystal surfaces. Solutions of LiBF4 and (C2H5)4NBF4 in propylene carbonate (PC) were used in this study. At small charge densities, the effect of frequency change is nearly of gravimetric nature. We propose a new method to determine the mass contribution to the resonance frequency shift due to adsorption of ions and accompanying solvent molecules, revealing different ion/solvent population ratios for Li+, (C2H5)4 N+ and BF4 − ions correlated to the ion solvation ability. The EQCA model applied describes the change in the frequency and in resonance peak width in terms of dimensional changes of large carbon particles (bumps) and of pseudo-uniform layers of smaller particles mixed with PVdF. The type of oscillation energy dissipation in composite carbon electrodes with PVdF binder strongly depends on non-uniform potential-induced deformations of electrode particles, and this suggests a strong effect of solvent nature on the mechanical properties of polymeric binders. EQCA may provide important information on the role of polymeric binders during cycling of composite electrodes both for supercapacitors and for Li-ion batteries electrodes.

A new approach, involving a two-fluid model, has been developed to interpret the quartz crystal microbalance response of adsorbed viscoelastic polymers. The model utilizes the Navier-Stokes-Brinkmann equation to describe the motion of a porous, semirigid, viscoelastic polymer-brush film with a viscous solvent flowing through it. The two phases, solid (polymer brush) and liquid (solvent mixture), hydrodynamically interact with each other, as represented by means of a Darcy term with a characteristic correlation factor. The two-fluid model is used to estimate structural changes in polymer brushes consisting of the copolymers poly(L-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG) or poly(L-lysine)-graft-dextran (PLL-g-dextran) adsorbed on an amorphous SiO2-coated quartz surface in aqueous solutions of glycerol, ethylene glycol (EG), and dimethyl sulfcodde (DMSO). Layer thickness, polymer volume fraction, and shear modulus of the polymer films with varying co-solvent concentration are determined with this approach. It was found that preferential hydrogen-bonding interactions of solvent mixtures with the polymers leads to variation in the structural properties of the polymer brushes upon changing the co-solvent composition. Furthermore, the conformation of polymer brushes in solvent mixtures is influenced by the solvent-solvent interactions, which can be explained in terms of the free energy of solvent mixing.

A novel approach to tracking intercalation-induced phase transitions in Li-ion battery materials demonstrated herein consists of simultaneous analysis of intercalation charge and the accompanying mechanical (geometric) changes in a microarray electrode composed of LixFePO4 intercalation particles probed by the electrochemical quartz-crystal admittance (EQCA) method. A recently elaborated approach to population dynamics of active (phase-transforming) nanoparticles(1) has been used here for modeling current transients applying small potential steps to LixFePO4 electrodes. The number fraction of (phase) transformed particles thus calculated was directly compared with the changes in the effective thickness and permeability length of the electrode coating derived by EQCA. Geometric changes of thin active mass originating from different molar volumes of the parent and transformed phase result in nonuniform deformations of intercalation particles. This study confirms the collective behavior of LixFePO4 intercalation particles during electrochemically induced phase transition. The use of EQCA as a highly precise and sensitive probe of mass and geometric changes in the electrode layer of intercalation particles paves the way for dynamic in situ studies of nonuniform intercalation particles deformations which can hardly be assessed by other available techniques.