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All solid-state batteries (ASSBs) with ceramic electrolytes and alkali metal anodes are a potential future energy storage technology for vehicle electrification and smart grids. However, uncontrollable dendrite growth toward ultimate short circuiting in solid electrolytes (SEs) has become a serious concern in the design of long-cycle, safe ASSBs, and the underlying mechanism has remained unclear. Here through multiscale imaging and morphodynamic tracking we show that Na dendrites grow in β′′-Al2O3 SEs through an alternating sequence of Na deposition and crack propagation. Atomic-scale imaging evidenced that electrochemical cycling causes massive delamination cracking along the Na+ conduction planes, accompanied by the closure of neighboring conduction channels. In situ SEM observations revealed a dynamic interplay between Na deposition and crack propagation: Na deposition accumulates mechanical stress that induces cracking; cracking releases the local stress, which promotes further Na deposition. Thus, Na deposition and cracking alternatingly proceed until short circuits take place. A multiscale phase-field model is developed to recapitulate the morphodynamics of Na dendrite growth, predicting the tree-like fractal morphology of the growing dendrites. Our findings suggest that decoupling between Na deposition and cracking represents an important route to mitigate uncontrollable dendrite growth in ASSBs.

The very high ionic conductivity of Li10GeP2S12 (LGPS) solid electrolyte (SE) makes it a promising candidate SE for solid-state batteries in electrical vehicles. However, chemomechanical failure, whose mechanism remains unclear, has plagued its widespread applications. Here, we report in situ imaging lithiation-induced failure of LGPS SE. We revealed a strong size effect in the chemomechanical failure of LGPS particles: namely, when the particle size is greater than 3 μm, fracture/pulverization occurred; when the particle size is between 1 and 3 μm, microcracks emerged; when the particle size is less than 1 μm, no chemomechanical failure was observed. This strong size effect is interpreted by the interplay between elastic energy storage and dissipation. Our finding has important implications for the design of high-performance LGPS SE, for example, by reducing the particle size to less than 1 μm the chemomechanical failure of LGPS SE can be mitigated.

Layered cathode materials are commonly used in lithium and sodium ion batteries, but they are prone to degradation under electrochemical cycling during battery operation. Here we report a new type of degradation mechanism through the electrochemically induced mechanical buckling and delamination cracking of intercalation layers in a P2 Na0.7-Ni0.3Mn0.6Co0.1O2 (Na-NMC) cathode material. Kinks form in the delaminated layers due to severe local bending, and each kink consists of a vertical array of dislocations, resulting from an easy slip between transition metal oxide layers. In situ mechanical compression experiments directly reveal the kink formation due to strong mechanical anisotropy parallel and perpendicular to the intercalation layers in single-crystal Na-NMC. In situ electrochemical experiments indicate that kinks form during the desodiation process. Our results unveil a new mechanism of electrochemically induced mechanical degradation stemming from weak interlayer bonding in layered cathode materials. This work has broad implications for the mitigation of degradation associated with irreversible interlayer slip in layered cathode materials.

The increasing demand for safe and dense energy storage has shifted research focus from liquid electrolyte-based Li-ion batteries toward solid-state batteries (SSBs). However, the application of SSBs is impeded by uncontrollable Li dendrite growth and short circuiting, the mechanism of which remains elusive. Herein, we conceptualize a scheme to visualize Li deposition in the confined space inside carbon nanotubes (CNTs) to mimic Li deposition dynamics inside solid electrolyte (SE) cracks, where the high-strength CNT walls mimic the mechanically strong SEs. We observed that the deposited Li propagates as a creeping solid in the CNTs, presenting an effective pathway for stress relaxation. When the stress-relaxation pathway is blocked, the Li deposition-induced stress reaches the gigapascal level and causes CNT fracture. Mechanics analysis suggests that interfacial lithiophilicity critically governs Li deposition dynamics and stress relaxation. Our study offers critical strategies for suppressing Li dendritic growth and constructing high-energy-density, electrochemically and mechanically robust SSBs.

A challenging task in solid oxide fuel cells (SOFCs) is seeking for an alternative electrolyte, enabling high ionic conduction at relatively low operating temperatures, i.e., 300–600 °C. Proton‐conducting candidates, in particular, hold a significant promise due to their low transport activation energy to deliver protons. Here, a unique hierarchical TiO2‐SrTiO3@TiO2 structure is developed inside an intercalated TiO2‐SrTiO3 core as "yolk" decorating densely packed flake TiO2 as shell, creating plentiful nano‐heterointerfaces with a continuous TiO2 and SrTiO3 "in‐house" interfaces, as well the interfaces between TiO2‐SrTiO3 yolk and TiO2 shell. It exhibits a reduced activation energy, down to 0.225 eV, and an unexpectedly high proton conductivity at low temperature, e.g., 0.084 S cm−1 at 550 °C, confirmed by experimentally H/D isotope method and proton‐filtrating membrane measurement. Raman mapping technique identifies the presence of hydrogenated HO─Sr bonds, providing further evidence for proton conduction. And its interfacial conduction is comparatively analyzed with a directly‐mixing TiO2‐SrTiO3 composite electrolyte. Consequently, a single fuel cell based on the TiO2‐SrTiO3@TiO2 heterogeneous electrolyte delivers a good peak power density of 799.7 mW cm−2 at 550 °C. These findings highlight a dexterous nano‐heterointerface design strategy of highly proton‐conductive electrolytes at reduced operating temperatures for SOFC technology. [ABSTRACT FROM AUTHOR]

All‐solid‐state battery (ASSB) is a potential future energy storage technology to power the future world. However, the solid–solid contacts among the various components in ASSB often require a high stack pressure which is unrealistic in practical applications. Here it is shown that by carbon‐coating Sb2Se3 (Sb2Se3@C) nanorods, a record low stack pressure is attained, and the Sb2Se3@C electrode exhibits outstanding performance of 862 mAh g−1 over 50 cycles at 0.1 A g−1 when it is operated at 5 MPa stack pressure in an ASSB using LiIn anode and Li10Si0.3PS6.7Cl1.8 solid‐state electrolytes. Furthermore, a record high active material loading (the mass fraction of Sb2Se3@C being 0.7 in composite cathode) is achieved, and the Sb2Se3@C based ASSB delivers a reversible capacity of 2.6 mAh cm−2 at 0.1 A g−1 after 100 cycles. This work provides a strategy to significantly increase the cathode active material loading and dramatically reduce the stack pressure of ASSBs, which brings it one step closer toward the practical implementation of ASSBs for energy storage applications. [ABSTRACT FROM AUTHOR]

Metal sulfide (MS) is regarded as a promising candidate of the anode materials for sodium‐ion battery (SIB) with ideal capacity and low cost, yet still suffers from the inferior cycling stability and voltage degradation. Herein, the coordination relationship between the discharge product Na2S with the Na+ (NaPF6) in the electrolyte, is revealed as the root cause for the cycling failure of MS. Na+‐coordination effect assistants the dissolution of Na2S, further delocalizing Na2S from the reaction interface under the function of electric field, which leads to the solo oxidation of the discharge product element metal without the participation of Na2S. Besides, the higher highest occupied molecular orbital of Na2S suggest the facilitated Na2S solo oxidation to produce sodium polysulfides (NaPSs). Based on these, lowering the Na+ concentration of the electrolyte is proposed as a potential improvement strategy to change the coordination environment of Na2S, suppressing the side reactions of the solo‐oxidation of element metal and Na2S. Consequently, the enhanced conversion reaction reversibility and prolonged cycle life are achieved. This work renders in‐depth perception of failure mechanism and inspiration for realizing advanced conversion‐type anode. [ABSTRACT FROM AUTHOR]

Low Na+ and electron diffusion kinetics severely restrain the rate capability of MoS2 as anode for sodium‐ion batteries (SIBs). Slow phase transitions between 2H and 1T, and from NaxMoS2 to Mo and Na2S as well as the volume change during cycling, induce a poor cycling stability. Herein, an original Fe single atom doped MoS2 hollow multishelled structure (HoMS) is designed for the first time to address the above challenges. The Fe single atom in MoS2 promotes the electron transfer, companying with shortened charge diffusion path from unique HoMS, thereby achieving excellent rate capability. The strong adsorption with Na+ and self‐catalysis of Fe single atom facilitates the reversible conversion between 2H and 1T, and from NaxMoS2 to Mo and Na2S. Moreover, the buffering effect of HoMS on volume change during cycling improves the cyclic stability. Consequently, the Fe single atom doped MoS2 quadruple‐shelled sphere exhibits a high specific capacity of 213.3 mAh g−1 at an ultrahigh current density of 30 A g−1, which is superior to previously‐reported results. Even at 5 A g−1, 259.4 mAh g−1 (83.68 %) was reserved after 500 cycles. Such elaborate catalytic site decorated HoMS is also promising to realize other "fast‐charging" high‐energy‐density rechargeable batteries. [ABSTRACT FROM AUTHOR]