RESUMEN
Solid electrolytes hold the promise for enabling high-performance lithium (Li) metal batteries, but suffer from Li-filament penetration issues. The mechanism of this rate-dependent failure, especially the impact of the electrochemo-mechanical attack from Li deposition, remains elusive. Herein, we reveal the Li deposition dynamics and associated failure mechanism of solid electrolyte by visualizing the Li|Li7La3Zr2O12 (LLZO) interface evolution via in situ transmission electron microscopy (TEM). Under a strong mechanical constraint and low charging rate, the Li-deposition-induced stress enables the single-crystal Li to laterally expand on LLZO. However, upon Li "eruption", the rapidly built-up local stress, reaching at least GPa level, can even crack single-crystal LLZO particles without apparent defects. In comparison, Li vertical growth by weakening the mechanical constraint can boost the local current density up to A·cm-2 level without damaging LLZO. Our results demonstrate that the crack initiation at the Li|LLZO interface depends strongly on not only the local current density but also the way and efficiency of mass/stress release. Finally, potential strategies enabling fast Li transport and stress relaxation at the interface are proposed for promoting the rate capability of solid electrolytes.
RESUMEN
Constructing 3D skeletons modified with lithiophilic seeds has proven effective in achieving dendrite-free lithium metal anodes. However, these lithiophilic seeds are mostly alloy- or conversion-type materials, and they tend to aggregate and redistribute during cycling, resulting in the failure of regulating Li deposition. Herein, we address this crucial but long-neglected issue by using intercalation-type lithiophilic seeds, which enable antiaggregation owing to their negligible volume expansion and high electrochemical stability against Li. To exemplify this, a 3D carbon-based host is built, in which ultrafine TiO2 seeds are uniformly embedded in nitrogen-doped hollow porous carbon spheres (N-HPCSs). The TiO2@N-HPCSs electrode exhibits superior Coulombic efficiency, high-rate capability, and long-term stability when evaluated as compertitive anodes for Li metal batteries. Furthermore, the superiority of intercalation-type seeds is comprehensively revealed through controlled experiments by various in situ/ex situ electron and optical microscopies, which highlights the excellent structural stability and lithiophilicity of TiO2 nanoseeds upon repeated cycling.
Asunto(s)
Litio , Semillas , Carbono , ElectrodosRESUMEN
Despite the high specific capacity of silicon as a promising anode material for the next-generation high-capacity Li-ion batteries (LIBs), its practical applications are impeded by the rapid capacity decay during cycling. To tackle the issue, herein, a binder-grafting strategy is proposed to construct a covalently cross-linked binder [carboxymethyl cellulose/phytic acid (CMC/PA)], which builds a robust branched network with more contact points, allowing stronger bonds with Si nanoparticles by hydrogen bonding. Benefitting from the enhanced mechanical reliability, the resulting Si-CMC/PA electrodes exhibit a high reversible capacity with improved long-term cycling stability. Moreover, an assembled full cell consisting of the as-obtained Si-CMC/PA anode and commercial LiFePO4 cathode also exhibits excellent cycling performance (120.4 mA h g-1 at 1 C for over 100 cycles with 88.4% capacity retention). In situ transmission electron microscopy was employed to visualize the binding effect of CMC/PA, which, unlike the conventional CMC binder, can effectively prevent the lithiated Si anodes from cracking. Furthermore, the combined ex situ microscopy and X-ray photoelectron spectroscopy analysis unveils the origin of the superior Li-ion storage performance of the Si-CMC/PA electrode, which arises from its excellent structural integrity and the stabilized solid-electrolyte interphase films during cycling. This work presents a facile and efficient binder-engineering strategy for significantly improving the performance of Si anodes for next-generation LIBs.
RESUMEN
Cation-disordered rock-salt oxides with the O2-/O2n- redox reaction, such as Li1.2Mn0.4Ti0.4O2 (LMTO), are critical Li-rich cathode materials for designing high-energy-density batteries. Understanding the cationic-anionic redox accompanying the structural evolution process is really imperative to further improve the performance. In this work, the cationic-anionic redox and capacity degradation mechanism of carbon-coated LMTO during (dis)charge processes are elucidated by combining in situ X-ray diffraction, X-ray absorption near-edge spectroscopy, differential electrochemical mass spectrometry, transmission electron microscopy, and electrochemical analyses. It is concluded that the redox reaction of Mn2+/Mn4+ is quite stable, while the severe degradation is mainly caused by the O2-/O2n- redox process. Moreover, we clearly clarify how the cationic-anionic interplay governs sluggish kinetics, large polarization, and capacity fading in LMTO, and reveal for the first time that a certain amount of carbon coating is capable of suppressing the irreversible lattice oxygen loss and results in an encouraging cycling performance. In summary, we elucidate the degradation of cationic-anionic redox processes in cation-disordered cathode materials and propose strategies for adjusting the electronic/ionic conductivity of the electrodes to modulate the oxygen redox reactions, setting a new direction for the design of better cation-disordered oxides.