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Understanding the role of elastic strain in modifying catalytic reaction rates is crucial for catalyst design, but experimentally, this effect is often coupled with a ligand effect. To isolate the strain effect, we have investigated the influence of externally applied elastic strain on the catalytic activity of metal films towards the hydrogen evolution reaction (HER). We show that elastic strain tunes the catalytic activity in a controlled and predictable way. Both theory and experiment show strain controls reactivity in a controlled manner consistent with the qualitative predictions of the HER volcano plot and the d-band theory: Ni and Pt activity were accelerated by compression, while Cu activity was accelerated by tension. By isolating the elastic strain effect from the ligand effect, this study provides a greater insight into the role of elastic strain in controlling electrocatalytic activity., Comment: 24 pages, 9 figures

The effect of elastic strain on catalytic activity of platinum (Pt) towards oxygen reduction reaction (ORR) is investigated through de-alloyed Pt-Cu thin films; stress evolution in the de-alloyed layer and the mass of the Cu removed are measured in real-time during electrochemical de-alloying of (111)-textured thin-film PtCu (1:1, atom %) electrodes. In situ stress measurements are made using the cantilever-deflection method and nano-gravimetric measurements are made using an electrochemical quartz crystal nanobalance. Upon de-alloying via successive voltammetric sweeps between -0.05 and 1.15 V vs. standard hydrogen electrode, compressive stress develops in the de-alloyed Pt layer at the surface of thin-film PtCu electrodes. The de-alloyed films also exhibit enhanced catalytic activity towards ORR compared to polycrystalline Pt. In situ nanogravimetric measurements reveal that the mass of de-alloyed Cu is approximately 210 +/- 46 ng/cm2, which corresponds to a de-alloyed layer thickness of 1.2 +/- 0.3 monolayers or 0.16 +/- 0.04 nm. The average biaxial stress in the de-alloyed layer is estimated to be 4.95 +/- 1.3 GPa, which corresponds to an elastic strain of 1.47 +/- 0.4%. In addition, density functional theory calculations have been carried out on biaxially strained Pt (111) surface to characterize the effect of strain on its ORR activity; the predicted shift in the limiting potentials due to elastic strain is found to be in good agreement with the experimental shift in the cyclic voltammograms for the dealloyed PtCu thin film electrodes., Comment: 30 pages, 15 figures

Structural changes in amorphous LixSi during the initial lithiation of single crystal Si to amorphous LixSi were investigated as a function of Li flux and total charge using solid-state 7Li nuclear magnetic resonance (NMR) spectroscopy. Single crystal (100) Si wafers were used as a model system in this study, as the Li flux could be precisely controlled and uniformly distributed across the surface of the wafer. It was observed that peak shifts in solid-state 7Li NMR spectra varied as a function of the Li flux during the initial lithiation and stayed constant for samples of the same Li flux regardless of the total charge applied to the electrodes. We conclude from these results that the Li concentration in LixSi stays constant for a given flux regardless of the total coulombic charge applied to the electrode. The results from this study help better understand the kinetics, the reaction mechanisms, and the kinetic modeling of chemical reactions at the reaction front during the initial lithiation of Si (100)., Comment: 17 pages, 7 figures

Composite cathode coatings made of a high energy density layered oxide (Li1.2Ni0.15Mn0.55Co0.1O2, theoretical capacity ~377 mAh/g), polyvinylidene fluoride (PVdF) binder, and electron-conduction additives, were bonded to an elastic substrate. An electrochemical cell, built by pairing the cathode with a capacity-matched graphite anode, was electrochemically cycled and the real-time average stress evolution in the cathode coating was measured using a substrate-curvature technique. Features in the stress evolution profile showed correlations with phase changes in the oxide, thus yielding data complementary to in situ XRD studies on this material. The stress evolution showed a complex variation with lithium concentration suggesting that the volume changes associated with phase transformations in the oxide are not monotonically varying functions of lithium concentration. The peak tensile stress in the cathode during oxide delithiation was approximately 1.5 MPa and the peak compressive stress during oxide lithiation was about 6 MPa. Stress evolution in the anode coating was also measured separately using the same technique. The measured stresses are used to estimate the internal pressures that develop in a cylindrical lithium-ion cell with jelly-roll electrodes., Comment: 23 pages, 9 figures

A combination of experimental measurements and numerical simulations are used to characterize the mechanical and electrochemical response of thin film amorphous Si electrodes during cyclic lithiation. Parameters extracted from the experiment include the variation of elastic modulus and the flow stress as functions of Li concentration; the strain rate sensitivity; the diffusion coefficient for Li transport in the electrode; the free energy of mixing as a function of Li concentration in the electrode; the exchange current density for the Lithium insertion reaction; as well as reaction rates and diffusion coefficients characterizing the rate of formation of solid-electrolyte interphase layer at the electrode surface. Model predictions are compared with experimental measurements; and the implications for practical Si based electrodes are discussed., Comment: 37 pages, 11 figures

An in situ study of deformation, fracture, and fatigue behavior of silicon as a lithium-ion battery electrode material is presented. Thin films (100-200 nm) of silicon are cycled in a half-cell configuration with lithium metal foil as counter/reference electrode, with 1M lithium hexafluorophosphate in ethylene carbonate, diethylene carbonate, dimethyl carbonate solution (1:1:1, wt.%) as electrolyte. Stress evolution in the Si thin-film electrodes during electrochemical lithiation and delithiation is measured by monitoring the substrate curvature using the multi-beam optical sensing method. The stress measurements have been corrected for contributions from residual stress arising from sputter-deposition. An indirect method for estimating the potential errors due to formation of the solid-electrolyte-interphase layer and surface charge on the stress measurements was presented. The films undergo extensive inelastic deformation during lithiation and delithiation. The peak compressive stress during lithiation was 1.48 GPa. The stress data along with the electron microscopy observations are used to estimate an upper bound fracture resistance of lithiated Si, which is approximately 9-11 J/m^2. Fracture initiation and crack density evolution as a function of cycle number is also reported., Comment: 25 pages, 9 figures

We report real-time average stress measurements on composite silicon electrodes made with two different binders [Carboxymethyl cellulose (CMC), and polyvinylidene fluoride (PVDF)] during electrochemical lithiation and delithiation. During galvanostatic lithiation at very slow rates, the stress in a CMC-based electrode becomes compressive and increases to 70 MPa, where it reaches a plateau and increases slowly thereafter with capacity. The PVDF-based electrode exhibits similar behavior, although with lower peak compressive stress of about 12 MPa. These initial experiments indicate that the stress evolution in a Si composite electrode depends strongly on the mechanical properties of the binder. Stress data obtained from a series of lithiation/delithiation cycles suggests plasticity induced irreversible shape changes in contacting Si particles, and as a result, the stress response of the system during any given lithiation/delithiation cycle depends on the cycling history of the electrode. While these results constitute the first in-situ stress measurements on composite Si electrodes during electrochemical cycling, the diagnostic technique described herein can be used to assess the mechanical response of a composite electrode made with other active material/binder combinations., Comment: 22 pages, 8 figures

Charge lost per unit surface area of a silicon electrode due to the formation of solid-electrolyte-interphase (SEI) layer during initial lithiation was quantified, and the species that constitute this layer were identified. Coin cells made with Si thin-film electrodes were subjected to a combination of galvanostatic and potentiostatic lithiation and delithiation cycles to accurately measure the capacity lost to SEI-layer formation. While the planar geometry of amorphous thin films allows accurate calculation of surface area, creation of additional surface by cracking was prevented by minimizing the thickness of the Si film. The cycled electrodes were analyzed with X-ray photoelectron spectroscopy to characterize the composition of the SEI layer. The charge lost due to SEI formation measured from coin cell experiments was found to be in good agreement with the first-cycle capacity loss during the initial lithiation of a Si (100) crystal with planar geometry. The methodology presented in this work is expected to provide a useful practical tool for battery-material developers in estimating the expected capacity loss due to first cycle SEI-layer formation and in choosing an appropriate particle size distribution that balances mechanical integrity and the first cycle capacity loss in large volume expansion electrodes for lithium-ion batteries., Comment: 15 pages, 9 figures; Journal of Power Sources, 2012

Real-time stress evolution in a graphite-based lithium-ion battery negative-electrode during electrolyte wetting and electrochemical cycling is measured through wafer-curvature method. Upon electrolyte addition, the composite electrode rapidly develops compressive stress of the order of 1-2 MPa due to binder swelling; upon continued exposure, the stress continues to evolve towards an apparent plateau. During electrochemical intercalation at a slow rate, the compressive stress increases with the electrode's state-of-charge, reaching a maximum value of 10 - 12 MPa. There appears to be an approximate correlation between the rate of stress rise and the staging behavior of the lithiated graphite. De-intercalation at a slow rate results in a similar linear decrease in electrode stress. Tensile stress of a few MPa develops at the end of deintercalation in the first few cycles, after which the electrode remains under compressive stress only. Although higher peak stresses are seen at high C-rates, the dependence appears to be relatively weak (up to 5C). These measurements reveal, for the first time, the nature of stress evolution in practical lithium-ion-battery electrodes and provide useful data to quantify the driving force for mechanical damage that accrues in composite electrodes upon repeated cycling. While the reported results can serve as reference for calibrating theoretical and computational models to predict electrode stress and damage evolution, the methodology demonstrated can be used to measure stresses and characterize fatigue damage in any composite lithium-ion-battery electrode as well as optimize its microstructure to mitigate stress-related damage mechanisms., Comment: 22 pages, 8 figures; Journal of Power Sources, 201, 2012

We report in situ measurements of stress evolution in a silicon thin-film electrode during electrochemical lithiation and delithiation by using the Multi-beam Optical Sensor (MOS) technique. Upon lithiation, due to substrate constraint, the silicon electrode initially undergoes elastic deformation, resulting in rapid rise of compressive stress. The electrode begins to deform plastically at a compressive stress of ca. -1.75 GPa; subsequent lithiation results in continued plastic strain, dissipating mechanical energy. Upon delithiation, the electrode first undergoes elastic straining in the opposite direction, leading to a tensile stress of ca. 1 GPa; subsequently, it deforms plastically during the rest of delithiation. The plastic flow stress evolves continuously with lithium concentration. Thus, mechanical energy is dissipated in plastic deformation during both lithiation and delithiation, and it can be calculated from the stress measurements; we show that it is comparable to the polarization loss. Upon current interrupt, both the film stress and the electrode potential relax with similar time-constants, suggesting that stress contributes significantly to the chemical potential of lithiated-silicon., Comment: 12 pages, 3 figures

We report in situ measurement of biaxial moduli of a Si thin-film electrode as a function of its lithium concentration. During lithiation, biaxial compressive stress is induced in the Si film and it undergoes plastic flow. At any state-of-charge (SOC), a relatively small delithiation-relithiation sequence unloads and reloads the film elastically. From the stress and strain changes during a delithiation-relithiation cycle, the biaxial modulus of the film is calculated. Stress change is obtained by measuring the change in substrate curvature using a Multi-beam Optical Sensor; the elastic strain change is obtained from the change in SOC. By repeating these measurements at several different values of SOC, the biaxial modulus was seen to decrease from ca. 70 GPa for Li0.32Si to ca. 35 GPa for Li3.0Si. Such a significant reduction in elastic modulus has important implications for modeling stress evolution and mechanical degradation in Si-based anodes., Comment: 8 pages, 3 figures

An analysis of the dependence of electric potential on the state of stress of a lithiated-silicon electrode is presented. Based on the Larch\'e and Cahn chemical potential for a solid solution, a thermodynamic argument is made for the existence of the stress-potential coupling in lithiated-silicon; based on the known properties of the material, the magnitude of the coupling is estimated to be ca. 60 mV/GPa in thin-film geometry. An experimental investigation is carried out on silicon thin-film electrodes in which the stress is measured in situ during electrochemical lithiation and delithiation. By progressively varying the stress through incremental delithiation, the relation between stress change and electric-potential change is measured to be 100 - 120 mV/GPa, which is of the same order of magnitude as the prediction of the analysis. The importance of the coupling is discussed in interpreting the hysteresis observed in potential vs. state-of-charge plots, and the role of stress in modifying the maximum charge capacity of a silicon electrode under stress., Comment: 21 pages, 5 figures

We formulate the continuum field equations and constitutive equations that govern deformation, stress, and electric current flow in a Li-ion half-cell. The model considers mass transport through the system, deformation and stress in the anode and cathode, electrostatic fields, as well as the electrochemical reactions at the electrode/electrolyte interfaces. It extends existing analyses by accounting for the effects of finite strains and plastic flow in the electrodes, and by exploring in detail the role of stress in the electrochemical reactions at the electrode-electrolyte interfaces. In particular, we find that that stress directly influences the rest potential at the interface, so that a term involving stress must be added to the Nernst equation if the stress in the solid is significant. The model is used to predict the variation of stress and electric potential in a model 1-D half-cell, consisting of a thin film of Si on a rigid substrate, a fluid electrolyte layer, and a solid Li cathode. The predicted cycles of stress and potential are shown to be in good agreement with experimental observations., Comment: 46 pages, 5 figures

Crystalline to amorphous phase transformation during initial lithiation in (100) silicon-wafers is studied in an electrochemical cell with lithium metal as the counter and reference electrode. It is demonstrated that severe stress jumps across the phase boundary lead to fracture and damage, which is an essential consideration in designing silicon based anodes for lithium ion batteries. During initial lithiation, a moving phase boundary advances into the wafer starting from the surface facing the lithium electrode, transforming crystalline silicon into amorphous LixSi. The resulting biaxial compressive stress in the amorphous layer is measured in situ and it was observed to be ca. 0.5 GPa. HRTEM images reveal that the crystalline-amorphous phase boundary is very sharp, with a thickness of ~ 1 nm. Upon delithiation, the stress rapidly reverses, becomes tensile and the amorphous layer begins to deform plastically at around 0.5 GPa. With continued delithiation, the yield stress increases in magnitude, culminating in sudden fracture of the amorphous layer into micro-fragments and the cracks extend into the underlying crystalline silicon., Comment: 12 pages, 5 figures