From Nanoalloy to Nano-Laminated Interfaces for Highly Stable Alkali-Metal Anodes.

Metal anodes are considered the holy grail for next-generation batteries because of their high gravimetric/volumetric specific capacity and low electrochemical potential. However, several unsolved challenges have impeded their practical applications, such as dendrite growth, interfacial side reactions, dead layer formation, and volume change. An electrochemically, chemically, and mechanically stable artificial solid electrolyte interphase is key to addressing the aforementioned issue with metal anodes. This study demonstrates a new concept of organic and inorganic hybrid interfaces for both Li- and Na-metal anodes. Through tailoring the compositions of the hybrid interfaces, a nanoalloy structure to nano-laminated structure is realized. As a result, the nanoalloy interface (1Al2 O3 -1alucone or 2Al2 O3 -2alucone) presents the most stable electrochemical performances for both Li-and Na-metal anodes. The optimized thicknesses required for the nanoalloy interfaces for Li- and Na-metal anodes are different. A cohesive zone model is applied to interpret the underlying mechanism. Furthermore, the influence of the mechanical stabilities of the different interfaces on the electrochemical performances is investigated experimentally and theoretically. This approach provides a fundamental understanding and establishes the bridge between mechanical properties and electrochemical performance for alkali-metal anodes.

Ultra-Thin Lithium Silicide Interlayer for Solid-State Lithium-Metal Batteries.

All-solid-state batteries with metallic lithium (LiBCC ) anode and solid electrolyte (SE) are under active development. However, an unstable SE/LiBCC interface due to electrochemical and mechanical instabilities hinders their operation. Herein, an ultra-thin nanoporous mixed ionic and electronic conductor (MIEC) interlayer (≈3.25 µm), which regulates LiBCC deposition and stripping, serving as a 3D scaffold for Li0 ad-atom formation, LiBCC nucleation, and long-range transport of ions and electrons at SE/LiBCC interface is demonstrated. Consisting of lithium silicide and carbon nanotubes, the MIEC interlayer is thermodynamically stable against LiBCC and highly lithiophilic. Moreover, its nanopores (<100 nm) confine the deposited LiBCC to the size regime where LiBCC exhibits "smaller is much softer" size-dependent plasticity governed by diffusive deformation mechanisms. The LiBCC thus remains soft enough not to mechanically penetrate SE in contact. Upon further plating, LiBCC grows in between the current collector and the MIEC interlayer, not directly contacting the SE. As a result, a full-cell having Li3.75 Si-CNT/LiBCC foil as an anode and LiNi0.8 Co0.1 Mn0.1 O2 as a cathode displays a high specific capacity of 207.8 mAh g-1 , 92.0% initial Coulombic efficiency, 88.9% capacity retention after 200 cycles (Coulombic efficiency reaches 99.9% after tens of cycles), and excellent rate capability (76% at 5 C).

Fracture and Fatigue of Al2O3-Graphene Nanolayers.

Al2O3-graphene nanolayers are widely used within integrated micro/nanoelectronic systems; however, their lifetimes are largely limited by fracture both statically and dynamically. Here, we present a static and fatigue study of thin (1-11 nm) free-standing Al2O3-graphene nanolayers. A remarkable fatigue life of greater than one billion cycles was obtained for films <2.2 nm thick under large mean stress levels, which was up to 3 orders of magnitude longer than that of its thicker (11 nm) counterpart. A similar thickness dependency was also identified for the elastic and static fracture behavior, where the enhancement effect of graphene is prominent only within a thickness of ∼3.3 nm. Moreover, plastic deformation, manifested by viscous creep, was observed and appeared to be more substantial for thicker films. This study provides mechanistic insights on both the static and dynamic reliability of Al2O3-graphene nanolayers and can potentially guide the design of graphene-based devices.

Nanomechanical elasticity and fracture studies of lithium phosphate (LPO) and lithium tantalate (LTO) solid-state electrolytes.

All-solid-state batteries (ASSBs) have attracted much attention due to their enhanced energy density and safety as compared to traditional liquid-based batteries. However, cyclic performance depreciates due to microcrack formation and propagation at the interface of the solid-state electrolytes (SSEs) and electrodes. Herein, we studied the elastic and fracture behavior of atomic layer deposition (ALD) synthesized glassy lithium phosphate (LPO) and lithium tantalate (LTO) thin films as promising candidates for SSEs. The mechanical behavior of ALD prepared SSE thin films with a thickness range of 5 nm to 30 nm over suspended single-layer graphene was studied using an atomic force microscope (AFM) film deflection technique. Scanning transmission electron microscopy (STEM) coupled with AFM was used for microstructural analysis. LTO films exhibited higher stiffness and higher fracture forces as compared to LPO films. Fracture in LTO films occurred directly under the indenter in a brittle fashion, while LPO films failed by a more complex fracture mechanism including significant plastic deformation prior to the onset of complete fracture. The results and methodology described in this work open a new window to identify the potential influence of SSEs mechanical performance on their operation in flexible ASSBs.

Role of graphene in enhancing the mechanical properties of TiO2/graphene heterostructures.

Graphene has been integrated in many heterogeneous structures in order to take advantage of its superior mechanical properties. However, the complex mechanical response of heterogeneous films incorporating graphene is not well understood. Here, we studied the mechanical behavior of atomic layer deposition (ALD) synthesized TiO2/graphene, as a representative building block of a typical composite, to understand the mechanical behavior of heterostructures using an experiment-computational approach. The inclusion of graphene was found to significantly enhance the Young's modulus of TiO2/graphene hetero-films for films below a critical thickness of 3 nm, beyond which the Young's modulus approaches that of pure TiO2 film. A rule-of-mixtures was found to reasonably estimate the modulus of the TiO2/graphene hetero-film. Experimentally, these hetero-films were observed to fail via brittle fracture. Complimentary density functional theory and finite element modeling demonstrates strong adhesion at the graphene TiO2 interface and that graphene serves as a reinforcement, providing the hetero-film with an ability to sustain significantly high stresses at the point of failure initiation. The results and methodology described herein can contribute to the rational design of strong and reliable ultrathin hetero-films for versatile applications.