Lithium dendrites belong to the key challenges of solid-state battery research. They are unavoidable due to the imperfect nature of surfaces containing defects of a critical size that can be filled by lithium until fracturing the solid electrolyte. The penetration of Li metal occurs along the propagating crack until a short circuit takes place. It is hypothesized that ion implantation can be used to introduce stress states into Li6.4La3Zr1.4Ta0.6O12 which enables an effective deflection and arrest of dendrites. The compositional and microstructural changes associated with the implantation of Ag-ions are studied via atom probe tomography, electron microscopy, and nano X-ray diffraction indicating that Ag-ions can be implanted up to 1 µm deep and amorphization takes place down to 650-700 nm, in good agreement with kinetic Monte Carlo simulations. Based on diffraction results pronounced stress states up to -700 MPa are generated in the near-surface region. Such a stress zone and the associated microstructural alterations exhibit the ability to not only deflect mechanically introduced cracks but also dendrites, as demonstrated by nano-indentation and galvanostatic cycling experiments with subsequent electron microscopy observations. These results demonstrate ion implantation as a viable technique to design "dendrite-free" solid-state electrolytes for high-power and energy-dense solid-state batteries.

Solid-state homogeneous precipitation of nano-sized precipitates is one of the most effective processes to strengthen metal alloys, where the final density and size distribution of precipitates are largely controlled by the precipitation kinetics. Here, we report a strategy to inoculate the homogeneous precipitation of coherent precipitates to enhance the precipitation strengthening. Using the technologically important dilute Al-Zr alloys as an example, we demonstrate that an addition of a trace level of economical and readily available, non-L12 phase forming impurity atoms, X (X= Sn, Sb, Bi or Cd) and Si, can significantly enhance the diffusivity of Zr atoms and overturn the precipitation of L12-structured Al3Zr nanoparticles from the classical homogeneous nucleation and growth pathway into a nonclassical nucleation pathway: Al3Zr forms through the spontaneous formation of nano-scale local concentration fluctuations of Zr atoms on Zr-X(-Si)-vacancy clusters followed by a continuous increase of the concentration and chemical short-range ordering (CSRO). Such an impurity atoms induced heterogeneous nucleation based on a “spinodal decomposition like” mechanism dramatically accelerates the precipitation kinetics, leading to an order of magnitude higher number density of precipitates and a record high hardening efficiency of solute Zr atoms. By formulating the generalized selection principles for inoculating impurity elements, this inoculation strategy should be extendable to a broader range of materials to further explore the precipitation strengthening potentials.

SmallVolume 20, Issue 12 2470097 FrontispieceFree Access Deflecting Dendrites by Introducing Compressive Stress in Li7La3Zr2O12 Using Ion Implantation (Small 12/2024) Florian Flatscher, Florian Flatscher Department of Materials Science and Engineering, NTNU Norwegian University of Science and Technology, Trondheim, 7491 Norway Christian Doppler Laboratory for Solid-State Batteries, NTNU Norwegian University of Science and Technology, Trondheim, 7491 NorwaySearch for more papers by this authorJuraj Todt, Juraj Todt Chair of Materials Physics, Montanuniversität Leoben and Erich Schmid Institute for Materials Science, Austrian Academy of Sciences, Leoben, 8700 AustriaSearch for more papers by this authorManfred Burghammer, Manfred Burghammer European Synchrotron Radiation Facility, 6 rue Jules Horowitz, BP220, Grenoble, cedex 9, 38043 FranceSearch for more papers by this authorHanne-Sofie Søreide, Hanne-Sofie Søreide Department of Materials Science and Engineering, NTNU Norwegian University of Science and Technology, Trondheim, 7491 NorwaySearch for more papers by this authorLukas Porz, Lukas Porz Department of Materials Science and Engineering, NTNU Norwegian University of Science and Technology, Trondheim, 7491 NorwaySearch for more papers by this authorYanjun Li, Yanjun Li Department of Materials Science and Engineering, NTNU Norwegian University of Science and Technology, Trondheim, 7491 NorwaySearch for more papers by this authorSigurd Wenner, Sigurd Wenner SINTEF Industry, Department of Materials and Nanotechnology, Trondheim, 7465 NorwaySearch for more papers by this authorViktor Bobal, Viktor Bobal Department of Physics, University of Oslo, Oslo, 0316 NorwaySearch for more papers by this authorSteffen Ganschow, Steffen Ganschow Leibniz-Institut für Kristallzüchtung, Berlin , GermanySearch for more papers by this authorBernhard Sartory, Bernhard Sartory Materials Center Leoben, Leoben, 8700 AustriaSearch for more papers by this authorRoland Brunner, Roland Brunner Materials Center Leoben, Leoben, 8700 AustriaSearch for more papers by this authorConstantinos Hatzoglou, Constantinos Hatzoglou Department of Materials Science and Engineering, NTNU Norwegian University of Science and Technology, Trondheim, 7491 NorwaySearch for more papers by this authorJozef Keckes, Jozef Keckes Chair of Materials Physics, Montanuniversität Leoben and Erich Schmid Institute for Materials Science, Austrian Academy of Sciences, Leoben, 8700 AustriaSearch for more papers by this authorDaniel Rettenwander, Daniel Rettenwander Department of Materials Science and Engineering, NTNU Norwegian University of Science and Technology, Trondheim, 7491 Norway Christian Doppler Laboratory for Solid-State Batteries, NTNU Norwegian University of Science and Technology, Trondheim, 7491 NorwaySearch for more papers by this author Florian Flatscher, Florian Flatscher Department of Materials Science and Engineering, NTNU Norwegian University of Science and Technology, Trondheim, 7491 Norway Christian Doppler Laboratory for Solid-State Batteries, NTNU Norwegian University of Science and Technology, Trondheim, 7491 NorwaySearch for more papers by this authorJuraj Todt, Juraj Todt Chair of Materials Physics, Montanuniversität Leoben and Erich Schmid Institute for Materials Science, Austrian Academy of Sciences, Leoben, 8700 AustriaSearch for more papers by this authorManfred Burghammer, Manfred Burghammer European Synchrotron Radiation Facility, 6 rue Jules Horowitz, BP220, Grenoble, cedex 9, 38043 FranceSearch for more papers by this authorHanne-Sofie Søreide, Hanne-Sofie Søreide Department of Materials Science and Engineering, NTNU Norwegian University of Science and Technology, Trondheim, 7491 NorwaySearch for more papers by this authorLukas Porz, Lukas Porz Department of Materials Science and Engineering, NTNU Norwegian University of Science and Technology, Trondheim, 7491 NorwaySearch for more papers by this authorYanjun Li, Yanjun Li Department of Materials Science and Engineering, NTNU Norwegian University of Science and Technology, Trondheim, 7491 NorwaySearch for more papers by this authorSigurd Wenner, Sigurd Wenner SINTEF Industry, Department of Materials and Nanotechnology, Trondheim, 7465 NorwaySearch for more papers by this authorViktor Bobal, Viktor Bobal Department of Physics, University of Oslo, Oslo, 0316 NorwaySearch for more papers by this authorSteffen Ganschow, Steffen Ganschow Leibniz-Institut für Kristallzüchtung, Berlin , GermanySearch for more papers by this authorBernhard Sartory, Bernhard Sartory Materials Center Leoben, Leoben, 8700 AustriaSearch for more papers by this authorRoland Brunner, Roland Brunner Materials Center Leoben, Leoben, 8700 AustriaSearch for more papers by this authorConstantinos Hatzoglou, Constantinos Hatzoglou Department of Materials Science and Engineering, NTNU Norwegian University of Science and Technology, Trondheim, 7491 NorwaySearch for more papers by this authorJozef Keckes, Jozef Keckes Chair of Materials Physics, Montanuniversität Leoben and Erich Schmid Institute for Materials Science, Austrian Academy of Sciences, Leoben, 8700 AustriaSearch for more papers by this authorDaniel Rettenwander, Daniel Rettenwander Department of Materials Science and Engineering, NTNU Norwegian University of Science and Technology, Trondheim, 7491 Norway Christian Doppler Laboratory for Solid-State Batteries, NTNU Norwegian University of Science and Technology, Trondheim, 7491 NorwaySearch for more papers by this author First published: 22 March 2024 https://doi.org/10.1002/smll.202470097AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version 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Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract Solid-State Electrolytes Compressive stress is caused in Li6.4La3Zr1.4Ta0.6O12 by implanting Ag ions into the near surface region. This compressive stress enables the deflection of mechanically induced cracks, created via nano-indentation as well as growing dendrites during galvanostatic cycling experiments. This demonstrates ion implantation as a viable technique to design "dendrite-free" solid-state electrolytes. More In article number 2307515, Daniel Rettenwander and co-workers. Volume20, Issue12March 22, 20242470097 RelatedInformation

In this study the effect of a ramp up to artificial aging (AA) temperature in combination with natural aging (NA) was analyzed for two different industrial aluminium alloys. The alloys differ in their Mg/Si ratio as well as their copper (Cu) content. Both alloys have, however, a comparable amount of solute and dispersoid forming elements. The peak aged conditions of the alloys were investigated. NA prior to AA reduces the strength as compared with directly aged regardless of ramping. The hardness up to peak is very similar for conditions with and without the ramp if NA is performed, but for the Cu rich alloy a clear increase in peak hardness could be measured when ramped from the supersaturated solid solution (SSSS). The peak strength plateau is shorter for the ramped samples regardless of the NA time. Investigations by (scanning) transmission electron microscopy found longer but fewer precipitates when ramped from the SSSS and an increased precipitate number density when ramped after NA. Fewer hybrid-type precipitates and less overaged precipitates, e.g. B’, and more L/C could be found for all ramped conditions. Atom probe tomography measurements showed that more solute is left in the matrix between the precipitates when ramped directly from the SSSS. This was related to a lower precipitate number density.