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      • <i>In operando</i> X-ray diffraction strain measurement in Ni<sub>3</sub>Sn<sub>2</sub> – Coated inverse opal nanoscaffold anodes for Li-ion batteries

        Glazer, Matthew P.B.,Wang, Junjie,Cho, Jiung,Almer, Jonathan D.,Okasinski, John S.,Braun, Paul V.,Dunand, David C. Elsevier 2017 Journal of Power Sources Vol.367 No.-

        <P><B>Abstract</B></P> <P>Volume changes associated with the (de)lithiation of a nanostructured Ni<SUB>3</SUB>Sn<SUB>2</SUB> coated nickel inverse opal scaffold anode create mismatch stresses and strains between the Ni<SUB>3</SUB>Sn<SUB>2</SUB> anode material and its mechanically supporting Ni scaffold. Using <I>in operando</I> synchrotron x-ray diffraction measurements, elastic strains in the Ni scaffold are determined during cyclic (dis)charging of the Ni<SUB>3</SUB>Sn<SUB>2</SUB> anode. These strains are characterized using both the center position of the Ni diffraction peaks, to quantify the average strain, and the peak breadth, which describes the distribution of strain in the measured volume. Upon lithiation (half-cell discharging) or delithiation (half-cell charging), compressive strains and peak breadth linearly increase or decrease, respectively, with charge. The evolution of the average strains and peak breadths suggests that some irreversible plastic deformation and/or delamination occurs during cycling, which can result in capacity fade in the anode. The strain behavior associated with cycling of the Ni<SUB>3</SUB>Sn<SUB>2</SUB> anode is similar to that observed in recent studies on a Ni inverse-opal supported amorphous Si anode and demonstrates that the (de)lithiation-induced deformation and damage mechanisms are likely equivalent in both anodes, even though the magnitude of mismatch strain in the Ni<SUB>3</SUB>Sn<SUB>2</SUB> is lower due to the lower (de)lithiation-induced contraction/expansion.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Lithiation-induced strains quantified in a Ni<SUB>3</SUB>Sn<SUB>2</SUB> inverse opal anode <I>in operando</I>. </LI> <LI> Lithiation induces compressive average strains in Ni inverse opal scaffold. </LI> <LI> Ni inverse opal scaffold strain distribution reversibly broadens upon lithiation. </LI> <LI> Three measured volumes show similar cyclic strain averages and distributions. </LI> <LI> Ni<SUB>3</SUB>Sn<SUB>2</SUB> measured cyclic strains are similar to prior Si inverse opal anode studies. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

      • SCISCIESCOPUS

        Numerical and experimental investigation of (de)lithiation-induced strains in bicontinuous silicon-coated nickel inverse opal anodes

        Cho, H.H.,Glazer, M.P.B.,Xu, Q.,Han, H.N.,Dunand, D.C. Elsevier Science 2016 Acta materialia Vol.107 No.-

        <P>A volume expansion of up to similar to 310% occurs upon the lithiation of silicon in Si-coated nickel inverse opal anodes, which causes (de)lithiation-induced mismatch stresses and strains between the Si and Ni during battery cyclical (dis)charging. These (de)lithiation-induced mismatch strains and stresses are modeled via sequentially coupled diffusion- and stress-based finite element (FE) analysis, which takes the mechanical contact between the Si and Ni phases into account, as well as the complex geometry and material properties of the Si-coated Ni inverse opal anode system. During lithiation, compressive strains up to 0.2% are developed in the Ni scaffold since the Si active layer expands. A rapid recovery of these lithiation-induced mismatch strains occurs during subsequent delithiation, though full recovery is not achieved. Strain histories upon multiple (de)lithiation cycles vary with the choice of various mechanical contact conditions employed between the two phases, since the mechanical contact properties determine how the contacted phases interact mechanically. The numerically predicted strains are compared with experimental strain data collected in operando using X-ray diffraction. The simulated strain histories agree with the measured data, enabling the possibility of predicting mechanical performance and eventual degradation using only numerical modeling. In particular, the FE model indicates that plastic deformation occurs first in the lithiated Si active layer, then in the Ni scaffold. (C) 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.</P>

      • Size-dependent fracture of Si nanowire battery anodes

        Ryu, I.,Choi, J.W.,Cui, Y.,Nix, W.D. Pergamon Press 2011 Journal of the mechanics and physics of solids Vol.59 No.9

        We use a unique transmission electron microscope (TEM) technique to show that Si nanowires (NWs) with diameters in the range of a few hundred nanometers can be fully lithiated and delithiated without fracture, in spite of the large volume changes that occur in this process. By analyzing the stresses associated with lithiation and delithiation we conclude that the process does not occur by the growth of discrete crystalline phases; rather it occurs by amorphization of the Si NWs followed by diffusion of Li into the structure. By accounting for the large deformation associated with this process and by including the effects of pressure gradients on the diffusion of Li, we show that Si NWs with diameters less than about 300nm could not fracture even if pre-existing cracks were present in the NW. These predictions appear to be in good agreement with the experiment.

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